Planar chirality from the chiral pool: Diastereoselective anionic phospho-fries rearrangements at ferrocene

Article

pubs.acs.org/Organometallics

Planar Chirality from the Chiral Pool: Diastereoselective Anionic

Phospho-Fries Rearrangements at Ferrocene

Marcus Korb and Heinrich Lang*

Technische Universitat Chemnitz, Faculty of Natural Sciences, Institute of Chemistry, Inorganic Chemistry, Straße der Nationen 62,

̈

D-09107 Chemnitz, Germany

S

* Supporting Information

ABSTRACT: Exclusively, the anionic phospho-Fries rearrangement

has successfully been adopted on chiral ferrocenyl phosphates,

resulting in diastereomeric enriched 1,2-P,O-phosphonates (up to

95% de), which can further be converted to an enantiomerically

pure phosphane. A simple synthetic protocol for the preparation of

all starting materials based on several chiral-pool alcohols, chiral

(di)chlorophosphates, and the respective ferrocenyl phosphates is

reported. Optimized reaction conditions for the anionic phospho-

Fries rearrangement allow conversions at ambient temperature and

the use of variable lithium amid bases and diamines in hexane,

ensure virtually quantitative yields, and avoid side reactions. The

(bi)cyclic alkyl substituents result in air- and moisture-stable

compounds and furthermore allow the conversion of 1,1′-

substituted derivatives to 1,1′,2,2′-functionalized ferrocenes, which is reported for the ﬁrst time. Simultaneous rearrangements

at diferrocenyl phosphates to phosphinates and even 2-hydroxy-1,3-bis(phosphonato) ferrocenes and their workup under

ambient conditions can be performed. Single-crystal diﬀraction analysis allowed the determination of the absolute conﬁguration

of the planar chirality of two diastereomerically pure ferrocenes being the R_pisomers. Furthermore, strong T-shaped π−π

interaction patterns between aromatic C₅H₃and C₅H₄cycles for three compounds are observed.

However, the stereoselective formation of the desired

phosphane or phosphonate has not yet been achieved. A

possible stereoselective formation of the phosphonate could be

reached by a stereoselective proceeding of the Fries rearrange-

ment at ferrocene using cheap chiral auxiliaries and should be

preferred to a chiral resolution of the formed products, which,

however, is of minor importance, due to the high costs of the

chiral derivatizing agents, such as Mosher’s acid and chiral

amines.³

It is a fact that the Fries rearrangement does not proceed

stereoselectively for phenyl-based compounds,^4a,bdue to the

lack of planar chirality formed within the products. However,

molecules bearing asymmetric substituents^4c−fcan exhibit an ee

of 99% for concerted processes or innocent groups.

Regioselective examples are known on the basis of steric

eﬀects of further (bulky) substituents, electronic eﬀects in the

aromatic cycle,⁵or just one ortho position available for

lithiation, which also results in a high ee or de using chiral

substituents.^2c,6

Three examples for Fries (type) 1,3-X → C rearrangements

(X = O, S) have been reported in the literature so far, yielding

planar chiral compounds with a detectable ee/de (Scheme 1).

Diastereoselective reactions with the use of diaminocyclohexyl-

INTRODUCTION

■

Planar-chiral 1,2-substituted ferrocenes are of growing interest:

for example, as supporting ligands for catalytic C,C cross-

coupling reactions.¹The synthetic methodology is frequently

based on ortho-directed metalation and subsequent addition of

electrophiles.²However, only a small percentage of these

species contain heteroatoms, especially oxygen, directly bonded

at the 1,2-positions at the ferrocene backbone, due to the

absence of suitable electrophiles.^1aThis heteroelement, in

addition to phosphorus, was shown to act as a hemilabile

donating group enhancing the catalytic activity of such

molecules as supporting ligands in C,C cross-coupling

reactions.^1a

Recently, it was shown by our group that especially 1,2-P,O-

substituted ferrocenes are available via the anionic phospho-

Fries rearrangement, by preferably starting with ferrocenyl

phosphates.^1aThe respective rearranged racemic ferrocenyl

phosphonate was formed in 94% yield and, thus, with a high

regioselectivity. A further conversion to a 1,2-P,O phosphane,

which was used as a supporting ligand in the synthesis of

hindered biaryls, resulted in high yields of the appropriate

biaryls under mild reaction conditions and with low catalyst

loadings.^1aEnantiomerically pure 1,2-P,O phosphanes are

therefore also promising structural motifs for the adoption of

the chiral information from the planar ferrocene backbone to

the axial chiral biaryl.

Received: September 18, 2014

A

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

contrast, when the reaction conditions are adapted for

ferrocene, higher temperatures for the lithiation process (−30

°C) are required.^1aHowever, attempts to run the reaction

enantioselectively by using Simpkins’ base did not result in

enantiomerically enriched products.^1a,9,11Therefore, a diaster-

eoselective procedure is needed, which will be reported herein.

The known procedures for the synthesis of (chiral)

chlorophosphates are based on the reaction of the respective

alcohols in the presence of a base, such as triethylamine or

pyridine, and subsequent ﬁltration and distillation of the

product mixture.¹²Thus, the applied puriﬁcation process results

in a lower yield of the (di)chlorophosphates and high amounts

of ammonium salts.¹²We herein report on a straightforward,

high-yielding synthetic protocol including lithiation of cyclo-

hexyl (1a, Cy), (1R)-menthyl (1b, (1R)-Mt), (1S)-menthyl

(1c, (1S)-Mt), (1S)-borneyl (1d, Bo), (1R)-α-fenchyl (1e, Fn)

and (1S)-isopinocampheyl alcohols (1f, Ip) in diethyl ether as

the solvent at 0 °C and subsequent addition of POCl₃(Scheme

2). After removal of any lithium salt by simple ﬁltration over

Scheme 1. Synthesis of Planar-Chiral 1,2-Substituted

Aromatics via Anionic Fries Type (A) or Fries

Rearrangements (B, C; Tf = SO₂CF₃) Described in the

Literature⁷⁻⁹and Unknown Diastereoselective Anionic

Phospho-Fries Rearrangement for the Synthesis of 1,2-P,O-

Ferrocenes (D)

Scheme 2. Synthesis of Dialkylchlorophosphates 2a−f and

Further Reaction with FcOLi (3-Li) To Give

a

Dialkylferrocenyl Phosphates 4a−f

substituted phosphates (Scheme 1,A) results in an almost

diastereomerically pure 1,2-P,S ferrocene.⁷Establishing planar

chirality by using electron-withdrawing tricarbonyl chromium

units allows enantioselective rearrangements with a chiral base,

resulting in an acceptable ee of 54% (Scheme 1,B).⁸

Interestingly, during the reaction of 1,1′-ferrocenediyl bis-

(triﬂates) (Scheme 1,C), only the meso and not the racemic

compound is formed; therefore, the rearrangement at the

second cyclopentadienyl proceeds stereoselectively, induced by

the ﬁrst cyclopentadienyl.⁹

A stereoselective anionic phospho-Fries rearrangement has,

to the best of our knowledge, not been reported so far. We

herein report for the ﬁrst time on a stereoselective Fries

rearrangement to establish planar chirality at 1,2-P,O ferrocenes

using chiral pool alcohols. These species are easily available in

enantiomerically pure form, and they also can easily be

introduced to chiral ferrocenyl phosphates (Scheme 1,D),

which are promising educts for high-yielding anionic phospho-

Fries rearrangements as key compounds for planar chiral 1,2-

P,O phosphanes.

a

Legend: (i) (1) diethyl ether, BuLi (1 equiv), (2) POCl₃(0.5 equiv),

yields based on 1; (ii) (1) diethyl ether, 3, BuLi, −30 °C, (2) 2a−f,

yields based on 3.

Celite, the respective chlorophosphates 2a−f were obtained in

quantitative yields without the need for further puriﬁcation

(Experimental Section). Conversion of 2a−f to the ferrocenyl

phosphates 4a−f is realized by the lithiation of ferrocenol (3)

using butyllithium (=BuLi) and treatment of 3-Li with the

chlorophosphates 2a−f (Scheme 2). After the appropriate

workup, ferrocenes 4a−f could be isolated in good to excellent

yields (Scheme 2, Experimental Section).

However, the anionic phospho-Fries rearrangement of 4a−f

does not proceed under the reaction conditions which we have

reported recently for short-chain diethyl phosphate.^1aLow

yields obtained in the temperature range from −30 to 0 °C and

the beginning of ether cleavage at higher temperatures

prompted us to use nonpolar instead of polar solvents. The

required activity of the lithium base can be enabled by addition

of a diamine such as TMEDA (=tetramethylethylenediamine)

or chiral (−)-sparteine (=(−)-Spart) (Table SI1, Supporting

Information).

RESULTS AND DISCUSSION

■

The anionic phospho-Fries rearrangement enables an simple

access to 1,2-P,O-substituted compounds.^1aEspecially phenyl-

and naphthyl-based phosphonates, i.e. BINOL derivatives, are

known for their use as ligands in asymmetric catalysis.¹⁰The

general reaction conditions therefore include deprotonation

ortho to the phosphato moiety with a sterically demanding base

to avoid nucleophilic attack and stirring at low temperature for

a short time, followed by warming to room temperature. In

Using the optimized reaction conditions (hexane, diamine,

base, ambient temperature, 18 h), the desired rearrangement

products could be obtained in good to quantitative yields

(Table 1). It should be noted that the sterically more

demanding aliphatic substituents, in comparison to ethyl

groups,^1astabilize all phosphates as well as all further products

toward hydrolysis and, hence, these compounds can be handled

B

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

diastereomerically enriched products. However, when the

diamine from the achiral TMEDA is changed to the chiral

(−)-sparteine, no further positive inﬂuence on the de of 5e was

observed. Interestingly, when (−)-sparteine is used for the

rearrangement of the (1R)- and (1S)-menthyl phosphates 4b,c,

a double stereodiﬀerentiation is not detectable, due to an

enhanced de for both of the phosphonates 5b,c (Table 1,

Experimental Section). However, a mismatch situation occurs

for 5d−f, in which (−)-sparteine is not beneﬁcial for the

stereoselectivity.

Table 1. Anionic Phospho-Fries Rearrangement of

Ferrocenyl Phosphates 4a−f to O,O-Dialkyl (2-

Methoxyferrocenyl)phosphonates 5a−f

After the anionic phospho-Fries rearrangement, the resulting

hydroxy functionality is not limited to react with dimethyl

sulfate, as already shown recently.^1a

However, with the sterically more demanding alkyl groups a

limitation in reactivity might occur and, thus, chlorodiphenyl-

phosphane for the synthesis of 6a and chlorophosphates 6b−d

have been investigated, showing good (6b−d) to acceptable

(6a) yields (Scheme 3).

Scheme 3. Oxygen Functionalization after the Anionic

a

Phospho-Fries Rearrangement of 4a,e

a

Legend: (i) 4a, LDA, hexane, TMEDA, ClPPh₂/S₈, 25 °C, 18 h → 60

°C, 1 h; (ii) for 4a, LDA, hexane, TMEDA, 2a (6b) or 2e (6c), 25 °C,

18 h → 60 °C, 1 h, and for 4e, LTMP, hexane, TMEDA, 2e, 25 °C, 18

h → 60 °C, 1 h.

a

b

Isolated yields based on the respective phosphate 4. The de values

c

were determined by integration of ﬁtted ³¹P{¹H} NMR spectra. After

A further enhancement of the de of the formed 1,2-P,O-

ferrocene is possible by adding a chiral chlorophosphate, which

was investigated during the reaction of the fenchyl derivative 4e

by adding the respective fenchyl chlorophosphate 2e (Scheme

3). The resulting 2-phosphato ferrocenyl phosphonate 6d could

be obtained with a de of 95%,¹³due to a kinetically controlled

phosphate formation.¹⁴Reaction of nonchiral 4a with chiral 2e

also resulted in the diastereomerically enriched phosphate 6c

(de = 0.10), revealing the chirality of the chlorophosphates to

be the main reason for the kinetic phosphate formation. Single

crystals of recrystallized 5e and 6d exhibited the R_p

diastereomer in both cases (Figure 2), which we therefore

assume is the mainly formed diastereomer during the

rearrangement.

The 2-phosphato phosphonates 6b,d can undergo a further

anionic phospho-Fries rearrangement (Scheme 4). Using LDA

as the base, bis(phosphonates) 7a,b are formed in acceptable

(7a) to quantitative (7b) yields. Interestingly, the −OH

functionality in 7b cannot be converted into the respective

methyl ether, even using an excess of methyl sulfate at 60 °C.

single recrystallization.

in air and moisture for several weeks without a notable rate of

decomposition.

The kinetically controlled lithiation of ferrocenyl phosphates

4a−f resulted in a diastereomeric excess during the anionic

phospho-Fries rearrangement that depends on the demand of

the aliphatic substituents (Table 1). The fenchyl derivative 4e

therefore exhibits the highest de (80%) in phosphonate 5e, due

to the three methyl groups located closer to the oxygen-bonded

carbon in comparison with the other chiral pool alcohols. The

de of the rearrangement products 5a−f can easily be obtained

by the integration of ﬁtted signals in the ³¹P{¹H} NMR spectra

(Table 1) and is further inﬂuenced by the required diamine and

the base. Instead of LDA (=lithium diisopropylamide) the use

of the sterically more demanding base LTMP (=lithium

tetramethyl piperidide) resulted in an increased de for 5e

(LDA, de = 0.72; LTMP, de = 0.80). Recrystallization of 5e

further improved the de (0.90), which conﬁrms the fenchyl

substituent to be the most appropriate for establishing

C

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

c

Scheme 4. Consecutive Anionic Phospho-Fries Rearrangement of 6b,d to Bis(phosphonates) 7a−c

a

b

c

base = LDA. base = LTMP. Legend: (i): TMEDA, hexane, 18 h, 25 °C, Me₂SO₄, 60 °C, 1 h. Yields are based on 6b,d, respectively.

Bis(phosphonato) hydroxyferrocene 7b is stable toward air and

moisture and is most probably stabilized by intramolecular

hydrogen bridge bond formation to the phosphonato oxygen

atoms.¹⁵When the base is changed from LDA to LTMP, the

increased steric demand resulted in a signiﬁcantly lower yield of

7b. Additionally, the formation of 7c is observed with the

phosphonato substituents located at the 1,1′-positions and a

resulting de at 0.95, based on the de of the starting material

6d.¹⁶The lithiation exclusively occurs ortho to the phosphate

and not to the phosphonate substituent, due to the absence of

any ortho-methylated product, which indicates a less attractive

stabilization of the phosphonato in comparison to the

phosphato substituent.

Scheme 5. Synthesis and Anionic Phospho-Fries

Rearrangement of Alkyldiferrocenyl Phosphates 9a−d

c

In addition to a single anionic phospho-Fries rearrangement

at one aryl or ferrocenyl substituent, simultaneous rearrange-

ments are possible by replacing the alkyl with further aryl or

ferrocenyl substituents, which has been reported for up to

“triple-Fries” rearrangements.¹⁷For ferrocenyls, the simulta-

neous formation of two planar chiral ferrocene backbones

should be possible. With the chiral pool alcohols 1a,b,d,e as

starting materials, the dichlorophosphates 8a,b,d were synthe-

sized in a more simple “one-pot” approach, in comparison to

literature methodologies^12a(Scheme 5), including deprotona-

tion of the alcohols 1a,b,d,e and dropwise addition of the

formed alcoholates to an excess (>3 equiv) of POCl₃. After

removal of all volatiles dichlorophosphates 8a,b,d were

obtained as pure colorless oils in quantitative yields, avoiding

the need for further puriﬁcation. The alkyl diferrocenyl

phosphates 9a−d are accessible by reacting 8a−d with

deprotonated FcOLi (3-Li) (Scheme 5), whereas borneyl

derivative 9c was obtained as a side product during the

synthesis of 4d. However, the subsequent anionic phospho-

Fries rearrangement primarily yields the monorearranged

phosphonates 10a−d, as a mixture of the two possible isomers

with regard to the planar chirality. For 10b−d four

diastereomers were formed, due to the asymmetrically

substituted phosphorus, whereas 10a can be obtained as a

mixture of two diastereomers (de = 0.45) (Table SI2,

Supporting Information), which indicates that the positions at

the prochiral ferrocenes in the achiral phosphate are kinetically

not equal. Thus, a stereoselective anionic phospho-Fries

rearrangement is possible without a further chiral input. The

second rearrangement to phosphinates 11a−d is only observed

in low yields. Nevertheless, when the amount of base (>8

equiv) is increased for the nonchiral cyclohexyl-substituted 9a,

a quantitative conversion to the meso and the racemic isomers is

possible. After their separation, the racemic product is obtained

as the main diastereomer (de = 0.20).

a

b

c

Using 2 equiv of LDA. Using >8 equiv of LDA. Legend: (i) BuLi,

diethyl ether, >3 equiv of POCl₃, 25 °C, 18 h; (ii) BuLi, diethyl ether,

3, 8a,b,d (for 9a,b,d)/2d (for 9c), 25 °C, 18 h, yields are based on 3;

(iii) hexane, TMEDA, LDA (9a−c)/LTMP (9d), 18 h, Me₂SO₄, 60

°C, 1 h, yields for 10a−d and 11a−c are based on 9a−d; (iv) hexane,

TMEDA, LDA, 10d, 18 h, Me₂SO₄, 60 °C, 1 h, yield based on 10d.

Attempts to achieve 11d by a similar approach failed,

resulting in an almost quantitative formation of 10d. However,

lithiation of 10d resulted in the formation of the desired

phosphinate 11d. With regard to the stereoselectivity of the

rearrangement, the decreased number of chiral substituents

produced an unspeciﬁc mixture of isomers for 10b−d and

11b−d (Table SI2, Supporting Information). For 10d the

inﬂuence of the amount of the base was examined (Table SI2),

showing only a slight change in the integrals of the signals;

however, when the base was changed from LTMP to LDA a

signiﬁcant change of the integral of each signal in the ³¹P{¹H}

NMR was observed, but with none of the diastereomers formed

primarily. Borneyl derivative 11c, however, only resulted in the

formation of two diastereomers instead of four, indicating a

high stereoselectivity for one rearrangement. The disfavored

D

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

formation of phosphinates 11a−d as well as the decreased

diastereoselectivity can both be explained by the fact that

anionic Fries rearrangements, in general, are favored for

electron-poor compounds,^1a,5e,11asuch as phosphates, which

prevent the nucleophilic attack at the phosphorus atom due to

the higher acidity of the ferrocenyl protons.

The rearrangement products 10a−d are more electron rich

in comparison to phosphates 9a−d, due to the ferrocenyl

substituent. Furthermore, the lithium ion is well stabilized by

the hydroxy oxygen and the PO moiety,^15aand a further

lithiation is less desirable.

Recently, a 1,1′-substituted ferrocene bearing sterically

nondemanding ethyl groups, 13c, could not be converted to

the respective rearrangement compounds 14c and 15c, due to

its instability.^1aWhen the sterically more demanding (bi)cyclic

alcohols 1a,e were used, the stability of phosphates 13a,b as

well as of the corresponding phosphonates 14b and 15a,

respectively, is increased. However, the increased steric demand

requires stirring in hexane (13a, 4 h, 60 °C bath temperature)

or tetrahydrofuran (13b, 12 h, 80 °C bath temperature) to

complete the reaction of both hydroxyl moieties with the

chlorophosphates (Scheme 6). However, the conversion of

for the fenchyl substituent during this reaction. This is

attributed to the steric demand of the chiral fenchyl

substituents or an unfavorable stabilization of the lithiated

species, which prevents the rearrangement to 15b.

Furthermore, the highly diastereomerically enriched phos-

phonate 5e could be converted to 16, revealing that the

recently reported reaction conditions for the reduction of

ferrocenyl phosphonates can be adopted on sterically more

demanding derivatives (Scheme 7).^1a,18

Scheme 7. Conversion of Phosphonate 5e to

a

Enantiomerically Pure (R_p)-17

Scheme 6. Synthesis of 1,1′-Ferrocenediyl Phosphates 13a−c

and Anionic Phospho-Fries Rearrangement to Phosphonates

a

14a−c and 15a−c

a

Legend: (i) (1) Li[AlH₄] (>3 equiv), Me₃SiCl (>3 equiv),

tetrahydrofuran, 25 °C, (2) 5e, 50 °C, 12 h; (ii) PhI (2 equiv),

K₃PO₄(2 equiv), [Pd(dppf)Cl₂] (4 mol %), toluene, 110 °C, 12 h,

65%, yield based on 5e; (iii) crystallization from hexane; (iv)

atmospheric conditions, 2 weeks, 95/5 (v/v) hexane/^tBuOMe.

When 16 was used under palladium-catalyzed Stelzer P,C

cross-coupling reaction conditions,^1a,19the respective diphe-

nylphosphino ferrocene 17 could be obtained in 65% yield (ee

= 0.80). Single recrystallization from hexane increased the ee to

>0.99, evidenced by chiral HPLC (Figure SI7, Supporting

Information). Furthermore, single crystals of the corresponding

enantiopure phosphine oxide 18 could be obtained from a

sample solution of 17 after standing for 2 weeks under

atmospheric conditions (Scheme 7), revealing the expected

planar chiral R isomer (Figure 4).

All compounds were analyzed using ¹H, ¹³C{¹H} and

³¹P{¹H} NMR spectroscopy, resulting in complex spectra,

due to the signals of several formed diastereomers, especially

for 5a−f, 10a−d, and 11a−d. In general, the ³¹P{¹H} NMR

shift is a meaningful indication of a successful conversion of

chlorophosphates 2 and 8 (2.3 (2a) to 5.9 (2e); 5.7 (8a) to 8.4

ppm (8d)) to phosphates 4 and 9 (−4.3 (4e) to −6.8 (4a); −

9.8 (9c,d) to −10.9 ppm (9a)) and 13 (−6.9 (a) to −4.3 ppm

(b)). Furthermore, the phosphato substituents in ferrocenes

6a−d (−3.5 (6d) to −7.4 ppm (6b)) and 14b (−4.5 ppm)

exhibit similar values (Experimental Section). The distinction

between phosphonates 10a−d (19.8 (10b) to 21.5 ppm (10d))

and phosphinates 11a−d (34.2 (11a) to 38.0 ppm (11d)) is

also rather simple by comparing with the chemical shifts of

phosphonates 5a−f and 7a−c (20.6 (5b) to 23.2 ppm (5d);

19.8(7a) to 25.8 ppm (7b)) and 15a (20.8 ppm), due to the

formation of up to four diastereomers.

a

Legend: (i) BuLi, for 13a, hexane, 2a, 12 h, 60 °C, 4 h, for 13b,

tetrahydrofuran, 2e, 12 h, 80 °C, 12 h, for 13c, NEt₃, ClP(O)(OEt)₂,

CH₂Cl₂, −20 °C;^1a(ii) LDA (R = Cy)/LTMP (R = Fn), TMEDA,

hexane, 25 °C, 18 h, Me₂SO₄, 50 °C, 1 h, for 13c, LDA,

tetrahydrofuran, −30 °C, Me₂SO₄.

cyclohexyl-substituted 13a proceeds to the expected double-

rearranged product 15a as a mixture of both diastereomers with

a de of 13%. Obviously, the lithiation of the C₅H₄cycle is

inﬂuenced by the conﬁguration established at the ﬁrst

cyclopentadienyl ring. Using the reaction protocol for

diastereomerically enriched fenchyl derivatives, a slight increase

of the de (0.84) of 14b in comparison to that for singly

substituted 5e (de = 0.80) could be detected (Scheme 6).

Nevertheless, the rearrangement product containing phospho-

nates at both cyclopentadienyls (15b) could not be obtained

A further indicator of a successful anionic phospho-Fries

1

rearrangement is the J_C,Pcoupling constant of the ferrocenyl

E

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

C−P bond, which displays a signiﬁcant decrease from 217(2)

Hz for phosphonates to 160(3) Hz for the more electron rich

phosphinates 11a−d. The veriﬁcation of the 1,1′-substitution

pattern in the unexpectedly formed bis(phosphonate) 7c in

comparison to bis(phosphonate) 7b (Scheme 4) is indicated by

1

the absence of the C₅H₅signal in the H and in the ¹³C{¹H}

NMR spectra and the appearance of the ³¹P{¹H} resonances as

singlets at 21.3 and 23.8 ppm, in comparison with 7b, where

3

doublets for both signals (21.3 and 25.8 ppm; J_P,P= 3.7 Hz)

are characteristic. Additional 2D ³¹P/¹H experiments allow the

assignment of three (21.3 ppm) and four (23.8 ppm) ¹H signals

to the respective phosphorus resonance (Figure SI1, Support-

ing Information). Since 11a can be separated into both of its

diastereomers, the classiﬁcation as a meso (pseudochiral

phosphorus atom) and a racemic compound (prochiral P

atom and ferrocenyl substituents) can be realized by the fact

that the racemic stereoisomers exhibits double signal sets for all

1

atoms in the ¹³C{¹H} (Supporting Information) and H NMR

spectra.

The molecular structures of 4a,b,e, 5e, 6d, 9b, 10a,c,d, and

18 in the solid state have been determined by single-crystal X-

ray diﬀraction analysis (Figures 1−4). Suitable crystals were

obtained by crystallization from hexane solutions at ambient

temperature. The ORTEP diagrams with selected bond lengths,

bond angles, and torsion angles are shown in Figures 1−4.

Compounds with cyclohexyl substituents (4a, 10a) crystallize

in the noncentrosymmetric space group P2₁/c, whereas the

chiral substituents lead to the chiral Sohncke space groups^20,21

P1 (4e), P2₁2₁2₁(4b, 5e, 18), P2₁(9b, 10c,d), and C2 (6d)

with one (4a,b, 5e, 9b, 10a, 18) or two molecules (4e, 6d,

10c,d) in the asymmetric unit. Thus, the absolute conﬁguration

for 5e, 6d, and 18 could be determined as the R_pdiastereomer

(Figures 2 and 4), whereas for 10c,d a mixture of the R_p,S^Pand

the S_p,R^Pdiastereomers emerges (Figure 3). The two molecules

of 4e in the asymmetric unit diﬀer from each other in the

conformation of the PO bond directed to either the right or

left side with regard to the plane view of the ferrocene (Figure

1).

The conformation of the ferrocenyls is rather eclipsed

(angles in deg: 4a, 4.5(3); 4f, 6.7(6); 5f, 5.66(17); 6d, 8.6(3);

9b, 1.1(7); 10a, 8.3(2); 10d, 3.7(7), 8.5(7), 9.0(8); 18, 9.7(3))

or slightly deviates (angles in deg: 4b, 11.7(3); 6d, 11.5(2); 9b,

23.7(7); 10a, 10.5(2); 10d, 14.4(9)). For all singly substituted

(di)ferrocenyl phosphates 4a,b,e and 9b the phosphato moiety

is located above the binding cyclopentadienyl substituent (C−

C−O−P in deg: 4a, 18.0(6); 4b, 30.6(4); 4e, 72.6(8); 9b,

19.6(15), 89.8(9)), in contrast to the case for phosphonato

ferrocenyls, where instead the PO bond is directed toward

the metallocenyl backbone (C−C−PO in deg: 5e,

174.86(15); 6d, 158.5(3); 10a, 168.3(2); 10c, 175.9(4); 10d,

175.3(11)).

Figure 1. ORTEP diagram (50% probability level) of the molecular

structures of 4a (top left), 4b (top right), 4e (bottom left), and 9b

(bottom right) with the atom-numbering scheme. All hydrogen atoms

and further molecules in the asymmetric unit (4e) have been omitted

for clarity. Selected bond distances (Å), angles (deg), and torsion

angles (deg): for 4a, O1−P1 1.594(3), O2−P1 1.574(3), O3−P1

1.568(3), O4−P1 1.461(3), D1−Fe1 1.6511(6), D2−Fe1 1.6561(6),

O1−P1−O2 100.25(14), O1−P1−O3 102.84(14), O2−P1−O3

10400(15), D−Fe1−D 179.34(4), C5−C1−O1−P1 18.0(6); for 4b,

O1−P1 1.5799(18), O2−P1 1.5646(17), O3−P1 1.5671(19), O4−P1

1.4544(18), average D−Fe1 1.645, O1−P1−O2 101.50(9), O1−P1−

O3 101.23(10), O2−P1−O3 104.95(9), D−Fe1−D 178.60(3), C5−

C1−O1−P1 30.6(4); for 4f, O1−P1 1.596(5), O2−P1 1.563(5), O3−

P1 1.574(5), O4−P1 1.444(5), average D−Fe 1.65, O1−P1−O2

100.1(3), O1−P1−O3 101.8(3), O2−P1−O3 102.2(3), average D−

Fe−D 178, C2−C1−O1−P1 72.6(8), C35−C31−O5−P2 65.5(9);

9b, O1−P1 1.605(10), O2−P1 1.581(11), O3−P1 1.542(10), O4−P1

1.437(9), average D−Fe 1.65, O1−P1−O2 99.2(5), O1−P1−O3

103.6(6), O2−P1−O3 103.4(6), average D−Fe−D 178, C2−C1−

O1−P1 19.6(15), 12−C11−O2−P1 89.8(9). D1 denotes the

centroids of the C₅H₄and D2 of C₅H₅ligands.

top of the C₅H₃plane. Furthermore, a dimer between two

molecules is formed on the basis of weaker π−π interactions

between the two C₅H₅substituents (4.794(4)−4.901(2) Å;

Figure SI3, Supporting Information). The distance between the

similarly arranged ferrocenyls in phosphate 9b, in contrast,

exceeds the range of T-shaped π−π interactions (>5.0 Å); a

one-dimensional helical pattern is formed by the C₅H₅cycles

(4.571(7) Å) of both ferrocenyls (Figure SI4, Supporting

Information). A one-dimensional zigazg T-shaped π−π

interaction can be found between the C₅H₅cyclopentadienyls

in phosphonate 5e (4.7827(12) Å) in the solid state (Figure

SI5, Supporting Information).

In phosphane oxide 18 T-shaped intermolecular π−π

interactions can be observed between the C₅H₅and phenyl

rings (Figure SI6, Supporting Information), whereas intra-

molecular interactions are not present.

The PO bond is signiﬁcantly enlarged in 18 (PO

1.491(2) Å) in comparison to those in the phosphates and

phosphonates 4a,b,f, 5e, 6d, 9b and 10a,c,d (9b, 1.437(9) Å, to

10c, 1.469(4) Å), due to the more electron rich phenyl rings,

The methyl and further O-bonded substituents in the doubly

substituted ferrocenes 5e, 6d, 10a,c,d, and 18 are consequently

directed away from the remaining free electron pairs in the

vacant space between these two substituents. Interestingly, in

cyclohexyl phosphonate 10a an unfavorable axial conformation

is observed, in contrast to phosphate 4a, with the oxygen atom

located in the equatorial position.

Compounds 5e, 9b, and 10a,c,d exhibit T-shaped π−π

interactions between the aromatic cyclopentadienyl planes.

Obviously, strong intramolecular π contacts are present in

10a,c,d (4.556(3)−4.675(7) Å; Figure SI2, Supporting

Information) between the unsubstituted C₅H₅cycle and the

F

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

Figure 2. ORTEP diagram (50% probability level) of the molecular

structures of 5e (left) and 6d (right) with the atom-numbering

scheme. All hydrogen atoms, solvent molecules (6d, CH₂Cl₂), and a

second, similar molecule of 6d in the asymmetric unit have been

omitted for clarity. Selected bond distances (Å), angles (deg) and

torsion angles (deg): for 5e, P1−O2 1.4639(13), P1−O3 1.5770(12),

P1−O4 1.5915(13), average D−Fe 1.647, C1−P1−O2 117.06(8),

C1−P1−O3 99.70(8), C1−P1−O4 106.96(8), O3−P1−O4

101.40(7), O3−P1−O2 117.12(17), O4−P1−O2 112.68(7), C1−

C2−O1−C12 165.52(16), D−Fe1−D 178.97(3), C2−C1−P1−O3

174.86(15), C2−C1−P1−O4 79.96(17); for 6d, C1−P1 1.772(4),

O1−P1 1.589(2), O2−P1 1.575(2), O3−P1 1.464(2), P2−O4

1.592(2), P2−O5 1.453(3), P2−O6 1.567(3), P2−O7 1.558(3),

Fe−D1 1.6405(4), Fe−D2 1.6458(5), O1−P1−O2 101.43(11), O1−

P1−C1 105.46(13), O2−P1−C1 100.07(13), O6−P2−O7

103.58(14), O6−P2−O4 101.33(13), O4−P2−O7 101.98(13), C2−

C1−P1−O3 30.9(3), C2−C1−P1−O2 158.5(3), C2−C1−P1−O1

96.5(3), C1−C2−O4−P2 173.5(2). D1 denotes the centroids of the

C₅H₄and D2 of C₅H₅ligands.

Figure 4. ORTEP diagram (50% probability level) of the molecular

structure of (R_p)-18 with the atom-numbering scheme. All hydrogen

atoms have been omitted for clarity. Selected bond distances (Å),

angles (deg) and torsion angles (deg) for (R_p)-18: P1−O2 1.491(2),

P1−C1 1.787(3), P1−C_Ph1.787(3) and 1.808(3), D−Fe1 1.6485(6)

and 1.6516(6), D−Fe−D 176.44(4), C2−C1−P1−O2 6.3(4), C1−

C2−O1−C11 165.8(4) D denotes the centroids of the C₅H₄and

C₅H₅ligands.

The anionic phospho-Fries rearrangement was successfully

applied for the ﬁrst time for the synthesis of novel planar-chiral

1,2-P,O ferrocenes 5a−f, 6a−d, 7a−c, 10a−d, 11a,c,d, 14a, and

15b, resulting in diastereomerically enriched products (de up to

95%). Using easily available and enantiopure chiral pool

alcohols, i.e. (1R)- and (1S)-menthol, (1S)-borneol, (1R)-α-

fenchol, and (1S)-isopinocampheol, chiral (di)-

chlorophosphates 2a−f and novel (di)ferrocenyl phosphates

4a−f and 9a−d could be obtained by a straightforward

synthetic protocol. Treatment of the phosphates under

optimized reaction conditions (hexane, diamine, base, ambient

temperature) avoid the ether cleavage and yield the ferrocenyl

phosphonates in yields of up to 90% with 80% de for the

fenchyl derivative. This is due to the location of the three

methyl substituents close to the phosphate moiety and, thus,

the highest impact of the chirality on the lithiation process.

Further improvement by a subsequent stereoselective

phosphate formation increases the de to 95%, which is, to

the best of our knowledge, the only protocol for the synthesis

of diastereomerically pure planar chiral 1,2-P,O-ferrocenes

reported in the literature. This gives access to planar chiral

1,2-P,O ferrocenyl phosphanes and the investigations of their

behavior on the enantiomeric excess of atropselective biaryl

synthesis, which is currently under investigation. The absolute

conﬁguration of the planar chirality could be determined by

single-crystal X-ray diﬀraction analysis for two examples and

proved to be the R_pdiastereomer. Attempts to convert

diferrocenyl phosphates to double-rearrangement products

primarily yielded the single transformed compounds, even

with a de of 45% for nonchiral cyclohexyl substituents, which

has not been expected so far.

Figure 3. ORTEP diagram (50% probability level) of the molecular

structures of 10a (left), S_p,R^P-10c (middle), and S_p,R^P-10d (right) with

the atom-numbering scheme. All hydrogen atoms, solvent molecules

(10c, diethyl ether), and R_p,S^P-10c and R_p,S^P-10d, which are also

present in the asymmetric unit have been omitted for clarity. Selected

bond distances (Å), angles (deg) and torsion angles (deg): for 10a,

P1−O1 1.612(2), P1−O2 1.565(2), P1−O3 1.461(2), P1−C11

1.756(3), D−Fe1 1.6414(4)/1.6432(4), D−Fe2 1.6521(4)/

1.6571(4), O1−P1−C11 106.79(12), O2−P1−O2 99.42(11), C2−

C1−O1−P1 12.4(4); for 10c, P1−C1 1.753(6), P1−O2 1.611(3),

P1−O3 1.571(3), P1−O4 1.469(4), C1−P1−O2 106.5(2), C1−P1−

O1 103.5(2), O1−P1−O2 100.18(18), D−Fe1−D 175.43(64), D−

Fe2−D 179.63(36), average D−Fe 1.651, C16−C12−O2−P1 11.7(8);

10d, P1−O1 1.593(10), P1−O3 1.587(10), P1−O4 1.453(11), P1−

C11 1.768(8), O1−P1−C11 105.5(6), O3−P1−C11 104.1(6), O1−

P1−O3 99.6(5), C2−C1−O1−P1 179.7(9). D denotes the centroids

of the C₅H₄and C₅H₅ligands.

Single-crystal diﬀraction analyses exhibit intermolecular T-

shaped π−π interactions between C₅H₅substituents for several

compounds and strong intramolecular interactions for

ferrocenyl phosphonates (10a,c,d). Furthermore, the bulky

alkyl (bi)cycles allow the consecutive rearrangement to 2-

hydroxy-1,3-bis(phosphonates), as well as rearrangements of

1,1′-ferrocenediyl phosphates to compounds stable toward air

and moisture, which failed for the respective diethyl derivatives

recently.

and does not exceed the C₅H₃plane (C2−C1−P1O2

6.3(4)°). Interestingly, the PO moiety is rotated away from

the −OMe group, in contrast to the recently reported solid-

state structure of rac-17, whose free electron pair at the

phosphorus atom is directed toward the vacant space between

the 1,2-substituents.

G

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

mL, 32.0 mmol) were reacted as described in the general procedure

above.

Yield: 12.46 g (31.7 mmol, 99% based on 1b). H NMR (CDCl₃,

The sterically demanding fenchyl phosphonate 5e could

furthermore be converted into the respective enantiomerically

pure phosphane, whose racemic mixture has already been

investigated as an excellent supporting ligand for the synthesis

of hindered biaryls. These results give access to atropselective

reactions that are under current investigation.

1

δ): 0.80−0.85 (m, 6 H, CH₃), 0.86−0.89 (m, 2H), 0.90−0.96 (m,

12H, CH₃), 0.99−1.08 (m, 2H), 1.18−1.27 (m, 2H), 1.37−1.52 (m,

4H), 1.64−1.73 (m, 4H), 2.10−2.16 (m, 2H, CH(CH₃)₂), 2.29−2.36

(m, 2H, H6), 4.31−4.43 (m, 2H, H1). ¹³C{¹H} NMR (CDCl₃, δ):

15.77 (CH₃), 15.82 (CH₃), 20.89 (CH₃), 20.93 (CH₃), 21.84 (CH₃),

21.92 (CH₃), 22.91(CH₂), 25.56 (CH(CH₃)₂), 25.59 (CH(CH₃)₂),

31.60, 31.62, 33.89 (CH₂), 42.2 (d, ³J_C,P= 61.2 Hz, C6), 48.35, 48.38,

48.42, 48.44, 82.1 (d, ²J_C,P= 8.3 Hz, C1), 82.3 (d, ²J_C,P= 8.4 Hz, C1).

³¹P{¹H} NMR (CDCl₃, δ): 3.3. HRMS (ESI-TOF, m/z): calcd for

C₂₀H₃₈ClO₃P + Na 415.2139, found 415.2137 [M + Na]⁺(19%);

(C₂₀H₃₈ClO₃P)₂+ Na 807.4386, found 807.4484 [M + Na]⁺(100%).

Bis((1S)-menthyl)) Chlorophosphate (2c). (1S)-Menthol (1c; 5.00

g, 32.0 mmol), BuLi (12.8 mL, 32.0 mmol), and POCl₃(1.5 mL, 16.0

mmol) were reacted as described in the general procedure above.

Yield: 6.21 g (15.8 mmol, 99% based on 1c). ¹H NMR (CDCl₃, δ):

0.80−0.85 (m, 6H, CH₃), 0.86−0.89(m, 2H), 0.90−0.96 (m, 12H,

CH₃), 0.99−1.08 (m, 2H), 1.18−1.27 (m, 2H), 1.37−1.52 (m, 4H),

1.64−1.73 (m, 4H), 2.10−2.16 (m, 2H, CH(CH₃)₂), 2.29−2.36 (m,

2H, H6), 4.31−4.43 (m, 2H, H1). ¹³C{¹H} NMR (CDCl₃, δ): 15.77

(CH₃), 15.82 (CH₃), 20.89 (CH₃), 20.93 (CH₃), 21.84 (CH₃), 21.92

(CH₃), 22.91(CH₂), 25.56 (CH(CH₃)₂), 25.59 (CH(CH₃)₂), 31.60,

31.62, 33,89 (CH₂), 42.2 (d, ³J_C,P= 61.2 Hz, C6), 48.35, 48.38, 48.42,

EXPERIMENTAL SECTION

■

General Considerations. All reactions were carried out under an

atmosphere of nitrogen using standard Schlenk techniques. Tetrahy-

drofuran and hexane were puriﬁed by distillation from sodium/

benzophenone ketyl; diethyl ether was puriﬁed by distillation from

sodium; dichloromethane, N,N-dimethylformamide, N,N-diisopropyl-

amine, and acetonitrile were puriﬁed by distillation from calcium

hydride. For column chromatography either silica with a particle size

of 40−60 μm (230−400 mesh (ASTM), Fa. Macherey-Nagel) or

alumina with a particle size of 90 μm was used. The assignment and

labeling of the H and C atoms in the NMR of the (bi)cyclic aliphatic

substituents follows the IUPAC recommendations.¹⁹

Reagents. Butyllithium (BuLi) (2.5 M solution in hexane),

ferrocene, lithium tetramethylpiperidide (LTMP), (−)-sparteine, and

the alcohols 1a−f were purchased from commercial suppliers and used

without further puriﬁcation. POCl₃and TMEDA were distilled prior

to use.

2

1

48.44, 82.1 (d, J_C,P= 8.3 Hz, C1), 82.3 (d, J_C,P= 8.4 Hz, C1).

³¹P{¹H} NMR (CDCl₃, δ): 3.3. HRMS (ESI-TOF, m/z): calcd for

C₂₀H₃₈ClO₃P + Na 415.2139, found 415.2123 [M + Na]⁺(17%);

(C₂₀H₃₈ClO₃P)₂+ Na 807.4386, found 807.4431 [M + Na]⁺(100%).

Bis((1S)-borneyl) Chlorophosphate (2d). (1S)-Borneol (1d; 5.82 g,

37.7 mmol), BuLi (15.1 mL, 37.7 mmol), and POCl₃(1.8 mL, 18.9

mmol) were reacted as described in the general procedure above.

Yield: 7.25 g (16.7 mmol, 99% based on 1d). ¹H NMR (CDCl₃, δ):

0.887 (s, 6H, CH₃), 0.892 (s, 6H, CH₃), 0.924 (s, 3H, CH₃), 0.925 (s,

3H, CH₃), 1.28−1.37 (m, 6H), 1.70−1.80 (m, 4H, CH₂, H4), 1.89−

1.96 (m, 2H, CH₂), 2.32−2.42 (m, 2H, CH₂), 4.68−4.75 (m, 2H, H2).

¹³C{¹H} NMR (CDCl₃, δ): 13.1 (CH₃), 13.3 (CH₃), 18.75 (CH₃),

18.78 (CH₃), 19.9 (CH₃), 26.42 (CH₂), 26.47 (CH₂), 27.87 (CH₂),

Instruments. NMR spectra (500.3 MHz for H, 125.8 MHz for

¹³C{¹H} and 202.5 MHz for ³¹P{¹H} spectra) are reported with

chemical shifts in δ (ppm) downﬁeld from tetramethylsilane with the

1

solvent as the reference signal (chloroform-d: H at 7.26 ppm and

¹³C{¹H} at 77.00 ppm) or by external standards (³¹P{¹H} relative to

85% H₃PO₄0.0 ppm and P(OMe)₃139.0 ppm).

The HPLC measurements were performed with an UV detector

operating at 245 nm equipped with a Chiralcel OD-H column (4.6 ×

250 mm) using a 95/5 (v/v) hexane/^tBuOMe mixture (0.5 mL/min)

as the solvent. Retention times t are reported in minutes. The area of

the integrals is reported relative to 100%.

Single-Crystal X-ray Diﬀraction Analysis. Data were collected

at 110 K with graphite-monochromated Mo Kα radiation (λ = 0.71073

Å; 4a,b,e, 5e, 6d, 9b, 10a,d, and 18) or Cu Kα radiation (λ = 1.54184

Å; 10c). The molecular structures were solved by direct methods using

SHELXS-97²²and reﬁned by full-matrix least-squares procedures on

F²using SHELXL-97.^23,24All non-hydrogen atoms were reﬁned

anisotropically, and a riding model was employed in the treatment of

the hydrogen atom positions. Graphics of the molecular structures

have been created by using ORTEP.²⁵

Synthesis of Dialkyl Chlorophosphates 2a−e: General

Procedure. The respective alcohols 2a−f (2 equiv) were dissolved

in 10 mL of tetrahydrofuran; an equal volume of diethyl ether was

added, and the mixture was cooled to −30 °C. The dropwise addition

of BuLi (2 equiv) resulted in the formation of a colorless precipitate.

After the mixture was stirred for an additional 10 min at −30 °C,

POCl₃(1 equiv) was slowly added and the solution was warmed to

ambient temperature and stirred overnight. All volatiles were removed

under reduced pressure. The resulting residue was suspended in

diethyl ether and ﬁltered through a plug of Celite (minimum 5 cm)

with diethyl ether to remove the lithium salt. After removal of all

volatiles the respective chlorophosphates 2a−f were obtained as

colorless oils and used without further puriﬁcation.

3

27.90 (CH₂), 36.5 (d, J_C,P= 1.3 Hz, CH₂), 36.8 (d, J_C,P= 1.5 Hz,

CH₂), 44.8, 47.68 (C1/C7), 47.72 (C1/C7), 49.78−49.88 (m, C1/

C7), 86.86−86.98 (m, C2). ³¹P{¹H} NMR (CDCl₃, δ): 5.4. HRMS

(ESI-TOF, m/z): calcd for C₂₀H₃₄ClO₃P 411.1826, found 411.1850

[M]⁺.

Bis((1R)-α-fenchyl)) Chlorophosphate (2e). (1R)-α-Fenchol (1e;

6.01 g, 39.0 mmol), BuLi (15.6 mL, 39.0 mmol), and POCl₃(1.8 mL,

19.5 mmol) were reacted as described in the general procedure above.

Yield: 7.51 g (19.3 mmol, 99% based on 1e). ¹H NMR (CDCl₃, δ):

0.973 (s, 3H, CH₃), 0.977 (s, 3H, CH₃), 1.05−1.11 (m, 8H), 1.16 (s,

3H, CH₃), 1.17 (s, 3H, CH₃), 1.19−1.24 (m, 2H), 1.41−1.51 (m, 2H),

1.52−1.57 (m, 2H), 1.68−1.75 (m, 6H), 4.09 (dd, ³J_H,P= 11.2 Hz, J_H,H

= 1.8, 1H, H2), 4.14 (dd, ³J_H,P= 11.5 Hz, J_H,H= 1.8, 1H, H2). ¹³C{¹H}

NMR (CDCl₃, δ): 19.2 (CH₃), 19.4 (CH₃), 20.95 (CH₃), 20.98

(CH₃), 25.7−25.8 (m, C5/C6), 29.6 (CH₃), 29.9 (CH₃), 39.5−39.6

3

(m, C3), 40.8 (C7), 40.9 (C7), 47.9 (C4), 48.0 (C4), 49.3 (d, J_C,P

=

6.6 Hz, C1), 49.5 (d, ³J_C,P= 4.9 Hz, C1), 93.0−93.1 (m, C2). ³¹P{¹H}

NMR (CDCl₃, δ): 5.9. HRMS (ESI-TOF, m/z): calcd for

C₂₀H₃₄ClO₃P + Na 411.1826, found 411.1850 [M + Na]⁺(23%);

(C₂₀H₃₄ClO₃P)₂+ Na 799.3760, found 799.3864 [M₂+ Na]⁺(100%).

Bis((1S)-isopinocampheyl) Chlorophosphate (2f). (1S)-Isopino-

campheol (1f; 5.94 g, 38.5 mmol), BuLi (15.4 mL, 38.5 mmol), and

POCl₃(1.8 mL, 19.3 mmol) were reacted as described in the general

procedure above.

Dicyclohexyl Chlorophosphate (2a). Cyclohexanol 1a (6.75 mL,

64.1 mmol), BuLi (26 mL, 65 mmol), and POCl₃(3 mL, 32 mmol)

were reacted as described in the general procedure above. The

analytical data are in agreement with the data given in ref 26.

Yield: 8.90 g (31.7 mmol, 99% based on 1a). ¹H NMR (CDCl₃, δ):

1.25−1.42 (m, 6 H), 1.48−1.56 (m, 2 H), 1.59−1.66 (m, 4 H), 1.70−

1.81 (m, 4 H), 1.92−2.03 (m, 4 H), 4.54−4.61 (m, 2 H, H1). ¹³C{¹H}

Yield: 7.43 g (19.1 mmol, 99% based on 1f). ¹H NMR (CDCl₃, δ):

0.93 (s, 3H, H9/H10), 0.94 (s, 3H, H9/H10), 1.11−1.13 (m, 2H,

CH₂), 1.19 (s, 3H, H8), 1.20 (s, 3H, H8), 1.24 (s, 6H, H9/H10),

1.82−1.87 (m, 2H, H1), 1.94−2.00 (m, 2H, H5), 2.04−2.11 (m, 2H,

H4), 2.24−2.32 (m, 2H, H2), 2.36−2.44 (m, 2H, CH₂), 2.58−2.69

(m, 2H, H4), 4.84−4.93 (m, 2H, H3). ¹³C{¹H} NMR (CDCl₃, δ):

20.0 (C2), 20.2 (C2), 24.0 (C9/C10), 27.3 (C9/C10), 27.4 (C9/

C10), 33.7 (C7), 33.8 (C7), 36.3 (d, ³J_C,P= 2.9 Hz, C4), 36.7 (d, ³J_C,P

3

NMR (CDCl₃, δ): 23.3 (CH₂), 25.0 (CH₂), 32.7 (d, J_C,P= 4.7 Hz,

3

2

CH₂), 33.0 (d, J_C,P= 4.7 Hz, CH₂), 80.1 (d, J_C,P= 7.4 Hz, C1).

³¹P{¹H} NMR (CDCl₃, δ): 2.3.

Bis((1R)-menthyl) Chlorophosphate (2b). (1R)-Menthol (1b;

10.00 g, 64.0 mmol), BuLi (25.6 mL, 64.0 mmol), and POCl₃(3

H

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

= 2.8 Hz, C4), 38.21 (C6), 38.25 (C6), 41.38 (C5), 41.43 (C5), 44.95

(d, ³J_C,P= 6.7 Hz, C2), 45.14 (d, ³J_C,P= 6.5 Hz, C2), 47.6 (C1), 81.58

(C3), 81.63 (C3), 81.64 (C3), 81.7 (C3). ³¹P{¹H} NMR (CDCl₃, δ):

3.6. HRMS (ESI-TOF, m/z): calcd for C₂₀H₃₄ClO₃P + Na 411.1826,

found 411.1821 [M + Na]⁺(8%); (C₂₀H₃₄ClO₃P)₂+ Na 799.3760,

found 799.3807 [M₂+ Na]⁺(100%).

R1 = 0.0382, wR2 = 0.0879 (I > 2σ(I)), absolute structure parameter²⁸

−0.018(14).

Ferrocenyl Bis((1S)-menthyl) Phosphate (4c). Ferrocenol (3; 608

mg, 3.01 mmol), BuLi (1.3 mL, 3.25 mmol), and bis((1S)-menthyl)

chlorophosphate (2c; 1.18 g, 3.01 mmol) were reacted as described in

the general procedure. Puriﬁcation was realized by column

chromatography (silica, 4 × 10 cm column size) on silica using

dichloromethane (R_f= 0.37). Compound 4c was obtained as an

orange oil.

Synthesis of Dialkylferrocenyl Phosphates 4a−f, Alkyl

Diferrocenyl Phosphates 9a−d, and 1,1′-Ferrocenediyl Tet-

raalkyl Bis(phosphates) 13a,b: General Procedure. Ferrocenol

(3; 1 equiv) was dissolved in 10 mL of diethyl ether and cooled to −30

°C. Dropwise addition of BuLi (1 equiv) resulted in the formation of

an orange solid. The respective dialkyl chlorophosphate 2a−f (1

equiv) was added in a single portion, and the mixture was warmed to

room temperature and stirred overnight. All volatiles were removed

under reduced pressure. The residue was puriﬁed using column

chromatography on silica with diﬀerent eluents for each compound

(see below). All volatiles were removed under reduced pressure.

Dicyclohexyl Ferrocenyl Phosphate (4a). Ferrocenol (3; 1.00 g,

4.95 mmol), BuLi (2.2 mL, 5.5 mmol), and dicyclohexyl

chlorophosphate (2a; 1.54 g, 5.5 mmol) were reacted as described

in the general procedure. Puriﬁcation was realized by column

chromatography (silica, 4 × 7 cm column size) using a 97/3 (v/v)

dichloromethane/ethyl acetate mixture. Compound 4a was obtained

as an orange solid.

1

Yield: 1.40 g (2.51 mmol, 83% based on 3). H NMR (CDCl₃, δ):

0.77 (d, ³J_H,H= 7.0 Hz, 3H, CH₃), 0.82 (d, ³J_H,H= 7.0 Hz, 3H, CH₃),

0.83−0.87 (m, 2H), 0.89 (d, ³J_H,H= 7.0 Hz, 3H, CH₃), 0.91 (d, ³J_H,H

=

7.0 Hz, 3H, CH₃), 0.918 (d, ³J_H,H= 6.5 Hz, 3H, CH₃), 0.928 (d, ³J_H,H

= 6.5 Hz, 3H, CH₃), 0.95−1.05 (m, 2H), 1.11−1.18 (m, 2H), 1.229−

1.39 (m, 2H), 1.40−1.50 (m, 2H), 1.62−1.70 (m, 4H), 2.11 (dsept,

3

³J_H,H= 7.0 Hz, J_H,H= 2.5 Hz, 1H, CH(CH₃)₂), 2.17 (dsept, J_H,H

=

7.0 Hz, ³J_H,H= 2.5 Hz, 1H, CH(CH₃)₂), 2.21−2.30 (m, 2H), 3.85 (pt,

3+4

J

= 2.0 Hz, 2H, C₅H₄), 4.16−4.25 (m, 7H, C₅H₅, H1), 4.37 (dd,

H,H

J

_H,H= 3.4 Hz,, J_H,H= 1.5 Hz, 1H, C₅H₄), 4.44 (dd, J_H,H= 3.4 Hz, J_H,H=

1.5 Hz, 1H, C₅H₄). ¹³C{¹H}NMR (CDCl₃, δ): 15.8 (CH(CH₃)₂),

20.93 (CH(CH₃)₂), 20.95 (CH(CH₃)₂), 21.93 (CH(CH₃)), 21.99

(CH(CH₃)), 22.76 (CH₂), 22.85 (CH₂), 25.35 (CH(CH₃)₂), 25.43

4

(CH(CH₃)₂), 31.5 (d, J_C,P= 2.8 Hz, C5), 34.0 (CH₂), 42.5 (CH₂),

1

42.7 (CH₂), 48.45 (C2), 48.47 (C2), 48.51 (C2), 48.53 (C2), 60.0 (d,

Yield: 1.49 g (3.46 mmol, 70% based on 3). H NMR (CDCl₃, δ):

3

³J_C,P= 3.9 Hz, C₅H₄), 60.1 (d, J_C,P= 3.3 Hz, C₅H₄), 62.52 (C₅H₄),

1.23−1.38 (m, 6H, CH₂), 1.48−1.59 (m, 6H, CH₂), 1.70−1.80 (m,

4H, CH₂), 1.90−2.00 (m, 4H, CH₂), 3.84−3.89 (m, 2H, C₅H₄), 4.25

(s, 5H, C₅H₅), 4.38−4.44 (m, 4H, C₅H₄, H1). ¹³C{¹H} NMR (CDCl₃,

δ): 23.5 (CH₂), 25.1 (CH₂), 33.19 (CH₂), 33.23 (CH₂), 33.25 (CH₂),

2

62.55 (C₅H₄), 69.4 (C₅H₅), 79.78 (d, J_C,P= 6.8 Hz, C1), 79.79 (d,

²J_C,P= 6.8 Hz, C1), 117.8 (d, ²J_C,P= 4.3 Hz, C_C5H4−O). ³¹P{¹H} NMR

(CDCl₃, δ): −6.3.

3

33.29 (CH₂), 59.8 (d, J_C,P= 3.8 Hz, C₅H₄₂), 62.6 (C₅H₄), 69.4

Bis((1S)-borneyl) Ferrocenyl Phosphate (4d). Ferrocenol (3; 1.00

g, 4.95 mmol), BuLi (2.0 mL, 5.00 mmol), and bis((1S)-borneyl)

chlorophosphate (2d; 1.92 mg, 4.95 mmol) were reacted as described

in the general procedure. Puriﬁcation was realized by column

chromatography (silica, 4 × 15 cm) using a 95/5 (v/v) toluene/

diethyl ether mixture (R_f= 0.33). Compound 4d was obtained as an

orange solid.

2

(C₅H₅), 77.8 (d, J_C,P= 6.4 Hz, C1), 117.7 (d, J_C,P= 5.0 Hz, C−O).

³¹P{¹H} NMR (CDCl₃, δ): −6.8. HRMS (ESI-TOF, m/z): calcd for

C₂₂H₃₁FeO₄P 446.1304, found 446.1302 [M]⁺.

Crystal data for 4a: C₂₂H₃₁FeO₄P, M_r= 446.29, orthorhombic,

P2₁/c, λ = 0.71073 Å, a = 12.4882(12) Å, b = 18.1115(14) Å, c =

9.7751(9) Å, β = 111.679(11)°, V = 2054.5(3) Å³, Z = 4, ρ_calcd= 1.443

Mg m⁻³, μ = 0.838 mm⁻¹, T = 110.00(10) K, θ range 3.176−25.999°,

Yield: 1.26 g (2.27 mmol, 46% based on 3). Anal. Calcd for

9663 reﬂections collected, 4006 independent reﬂections (R_int

0.0719), R1 = 0.0822, wR2 = 0.2037 (I > 2σ(I)).

=

C₃₀H₄₃FeO₄P (554.48): C, 64.98; H, 7.82. Found: C, 64.88; H, 7.83.

1

Mp: 210−212 °C. H NMR (CDCl₃, δ): 0.86−0.90 (m, 18H, CH₃),

Ferrocenyl Bis((1R)-menthyl) Phosphate (4b). Ferrocenol (3; 1.03

g, 5.09 mmol), BuLi (2.1 mL, 5.25 mmol), and bis((1R)-menthyl)

chlorophosphate (2b; 2.00 g, 5.09 mmol) were reacted as described in

the general procedure. Puriﬁcation was realized by column

chromatography (silica, 4 × 10 cm column size) using dichloro-

methane as the eluent (R_f= 0.37). Compound 4b was obtained as an

orange solid.

1.22−1.30 (m, 6H), 1.66−1.69 (m, 2H), 1.70−1.77 (m, 2H), 1.91−

3,4

1.97 (m, 2H), 2.25−2.34 (m, 2H), 3.86 (pt,

J

= 1.9 Hz, 2H,

H,H

3,4

C₅H₄), 4.24 (s, 5H, C₅H₅), 4.39 (pt,

J

= 1.9 Hz, 2H, C₅H₄),

H,H

4.58−4.62 (m, 2H, H2). ¹³C{¹H} NMR (CDCl₃, δ): 13.28 (CH₃),

13.34 (CH₃), 18.8 (CH₃), 19.9 (CH₃), 26.4 (CH₂), 26.5 (CH₂), 27.9

3

(CH₂), 28.0 (CH₂), 36.8 (d, J_C,P= 1.7 Hz, C3), 37.1 (d, J_C,P= 1.8

3

Hz, C3), 44.8, 47.65 (C7), 47.66 (C7), 49.66 (d, J_C,P= 1.3 Hz, C1),

Yield: 3.00 g (4.64 mmol, 91% based on 3). Anal. Calcd for

C₃₀H₄₇FeO₄P (558.51): C, 64.51; H, 8.48. Found: C, 64.67; H, 8.69.

49.71 (d, ³J_C,P= 1.3 Hz, C1), 60.06 (d, ³J_C,P= 0.6 Hz, C₅H₄), 60.08 (d,

³J_C,P= 1.0 Hz, C₅H₄), 62.6 (C₅H₄), 69.4 (C₅H₅), 84.66 (d, ²J_C,P= 2.2

1

3

Mp: 79−80 °C. H NMR (CDCl₃, δ): 0.77 (d, J_H,H= 7.0 Hz, 3H,

CH₃), 0.82 (d, ³J_H,H= 7.0 Hz, 3H, CH₃), 0.83−0.87 (m, 2H), 0.89 (d,

³J_H,H= 7.0 Hz, 3H, CH₃), 0.91 (d, ³J_H,H= 7.0 Hz, 3H, CH₃), 0.918 (d,

2

Hz, C2), 84.71 (d, J_C,P= 2.3 Hz, C2), 117.7 (d, J_C,P= 4.6 Hz, C

_C5H4−O). ³¹P{¹H} NMR (CDCl₃, δ): −4.8. HRMS (ESI-TOF, m/z):

calcd for C₃₀H₄₃FeO₄P 554.2243, found 554.2242 [M]⁺.

³J_H,H= 6.5 Hz, 3H, CH₃), 0.928 (d, J_H,H= 6.5 Hz, 3H, CH₃), 0.95−

3

Bis((1R)-α-fenchyl) Ferrocenyl Phosphate (4e). Ferrocenol (3; 814

mg, 4.03 mmol), BuLi (1.65 mL, 4.13 mmol), and bis((1R)-α-fenchyl)

chlorophosphate (2e; 1.57 g, 4.04 mmol) were reacted as described in

the general procedure. Puriﬁcation was realized by column

chromatography (silica, 4 × 7 cm) using dichloromethane as the

eluent (R_f= 0.38). Compound 4e was obtained as an orange oil.

Yield: 1.85 g (3.33 mmol, 83% based on 3). Anal. Calcd for

C₃₀H₄₃FeO₄P (554.48): C, 64.98; H, 7.82. Found: C, 64.67; H, 7.86.

Mp: 64−68 °C. ¹H NMR (CDCl₃, δ): 0.91 (s, 3H, CH₃), 0.96 (s, 3H,

1.05 (m, 2H), 1.11−1.18 (m, 2H), 1.29−1.39 (m, 2H), 1.40−1.50 (m,

3

2H), 1.62−1.70 (m, 4H), 2.11 (dsept, J_H,H= 7.0 Hz, J_H,H= 2.5 Hz,

3

1H, CH(CH₃)₂), 2.17 (dsept, J_H,H= 7.0 Hz, J_H,H= 2.5 Hz, 1H,

CH(CH₃)₂), 2.21−2.30 (m, 2H), 3.86 (s, 2H, C₅H₄), 4.14−4.28 (m,

7H, C₅H₅, H1), 4.39 (s, 1H, C₅H₄), 4.44 (s, 1H, C₅H₄). ¹³C{¹H}

NMR (CDCl₃, δ): 15.8 (CH₃), 20.93 (CH₃), 20.94 (CH₃), 21.93

(CH₃), 21.99 (CH₃), 22.76 (CH₂), 22.85 (CH₂), 25.35 (CH), 25.42

4

(CH), 31.5 (d, J_C,P= 2.78 Hz, C5), 34.0 (CH₂), 42.5 (CH₂), 42.7

(CH₂), 48.44 (C2), 48.46 (C2), 48.50 (C2), 48.52 (C2), 60.0 (d, ³J_C,P

3

CH₃), 1.03−1.09 (m, 11H), 1.14−1.20 (m, 5H), 1.40−1.47 (m, 2H),

= 3.5 Hz, C₅H₄), 60.1 (d, J_C,P= 3.2 Hz, C₅H₄), 62.62 (C₅H₄), 62.64

3+4

(C₅H₄), 69.5 (C₅H₅), 79.8 (d, J_C,P= 6.9 Hz, C1), 118.6²⁷(d, J_C,P

=

2

1.49−1.53 (m, 2H), 1.68−1.75 (m, 6H), 3.85 (pt,

J

= 2.0 Hz,

H,H

4.3 Hz, C−O). ³¹P{¹H} NMR (CDCl₃, δ): −6.3. HRMS (ESI-TOF,

m/z): calcd for C₃₁H₄₅FeO₄P 568.2400, found 568.2453 [M]⁺.

Crystal data for 4b: C₃₀H₄₇FeO₄P, M_r= 558.50, orthorhombic,

P2₁2₁2₁, λ = 0.71073 Å, a = 7.3970(2) Å, b = 18.0245(4) Å, c =

21.8203(6) Å, V = 2909.24(13) Å³, Z = 4, ρ_calcd= 1.275 Mg m⁻³, μ =

0.606 mm⁻¹, T = 110.00(10) K, θ range 2.91−26.00°, 18502

reﬂections collected, 5616 independent reﬂections (R_int= 0.0590),

2H, C₅H₄), 3.97−4.01 (m, 2H, C₅H₄), 4.24 (s, 5H, C₅H₅), 4.41−4.45

(m, 2H, H2). ¹³C{¹H} NMR (CDCl₃, δ): 19.36 (CH₃), 19.36 (CH₃),

20.8 (CH₃), 21.1 (CH₃), 25.67 (C5/C6), 25.74 (C5/C6), 25.95 (C5/

C6), 25.98 (C5/C6), 29.9 (CH₃), 39.5 (d, ³J_C,P= 2.5 Hz, C3), 39.7 (d,

³J_C,P= 2.5 Hz, C3), 40.94 (CH₂), 40.97 (CH₂), 47.93 (C4), 47.95

(C4), 49.29 (C1), 49.33 (C1), 60.1−60.2 (m, C₅H₄), 62.6 (C₅H₄),

69.4 (C₅H₅), 91.0−91.2 (m, C2), 118.3 (HMBC, C_C5H4−O). ³¹P{¹H}

I

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

NMR (CDCl₃, δ): −4.3. HRMS (ESI-TOF, m/z): calcd for

C₃₀H₄₃FeO₄P 554.2243, found 554.2265 [M]⁺.

Crystal data for 9b: C₃₀H₃₇Fe₂O₄P, M_r= 604.26, monoclinic, P2₁,

λ = 0.71073 Å, a = 14.1041(13) Å, b = 5.8359(5) Å, c = 16.704(2) Å, β

= 92.648(9)°, V = 1371.4(2) Å³, Z = 2, ρ_calcd= 1.461 Mg m⁻³, μ =

1.149 mm⁻¹, T = 110.2(6) K, θ range 2.892−24.997°, 5764 reﬂections

collected, 4257 independent reﬂections (R_int= 0.0229), R1 = 0.0908,

wR2 = 0.1454 (I > 2σ(I)), absolute structure parameter²⁸0.02(6).

(1S)-Borneyl Diferrocenyl Phosphate (9c). The title compound was

obtained as a byproduct during the synthesis of 4d by reacting

ferrocenol (3; 1.00 g, 4.95 mmol), BuLi (2.0 mL, 5.00 mmol), and

bis((1S)-borneyl) chlorophosphate (2d; 1.92 mg, 4.95 mmol) as

described in the general procedure. Puriﬁcation was realized by

column chromatography (silica, 4 × 15 cm) using a 95/5 (v/v)

toluene/diethyl ether mixture (R_f= 0.43) as the eluent. Compound 9c

was obtained as an orange solid.

Crystal data for 4e: C₆₀H₈₆Fe₂O₈P₂, M_r= 1108.92, triclinic, P1, λ =

0.71073 Å, a = 11.6913(4) Å, b = 11.8705(4) Å, c = 12.0874(4) Å, α =

62.396(3)°, β = 77.005(3)°, γ = 69.734(3)°, V = 1390.35(9) Å³, Z = 1,

ρ_calcd= 1.324 Mg m⁻³, μ = 0.633 mm⁻¹, T = 110.0(10) K, θ range

3.106−24.997°, 10832 reﬂections collected, 7207 independent

reﬂections (R_int= 0.0156), R1 = 0.0425, wR2 = 0.1058 (I > 2σ(I)),

absolute structure parameter²⁸0.012(8).

Ferrocenyl Bis((1S)-isopinocampheyl) Phosphate (4f). Ferrocenol

(3; 830 mg, 4.11 mmol), BuLi (1.65 mL, 4.13 mmol), and bis((1S)-

isopinocampheyl) chlorophosphate (2f; 1.60 g, 4.11 mmol) were

reacted as described in the general procedure. Puriﬁcation was realized

by column chromatography (silica, 4 × 7 cm) using a 8/2 (v/v)

hexane/diethyl ether mixture as the eluent (R_f= 0.32). Compound 4f

was obtained as an orange oil.

Yield: 260 mg (0.43 mmol, 17% based on 3). Anal. Calcd for

C₃₀H₄₇FeO₄P (602.26): C, 59.83; H, 5.86. Found: C, 60.44; H, 6.00.

¹H NMR (CDCl₃, δ): 0.86 (s, 3H, CH₃), 0.87 (s, 3H, CH₃), 0.88 (s,

3H, CH₃), 1.22−1.31 (m, 3H, CH₂), 1.67 (t, J_H,H= 4.5 Hz, H4),

1.70−1.78 (m, 1H, CH₂), 1.89−1.95 (m, 1H, H6), 2.26−2.33 (m, 1H,

H3), 3.89−3.90 (m, 4H, C₅H₄), 4.261 (s, 5H, C₅H₅), 4.264 (s, 5H,

C₅H₅), 4.40−4.43 (m, 4H, C₅H₄), 4.64−4.68 (m, 1H, H2). ¹³C{¹H}

1

Yield: 1.90 g (3.43 mmol, 83% based on 3). H NMR (CDCl₃, δ):

0.92 (s, 3H, H9/H10), 0.93 (s, 3H, H9/H10), 1.107 (d, J_H,H= 9.9 Hz,

1H, H7), 1.112 (d, J_H,H= 9.9 Hz, 1H, H7), 1.16 (d, J_H,H= 7.4 Hz, 3H,

H8), 1.19 (d, J_H,H= 7.4 Hz, 3H, H8), 1.22 (s, 6H, H9/H10), 1.80−

1.84 (m, 2H, H1), 1.93−1.98 (m, 2H, H5), 1.99−2.04 (m, 2H, H4),

NMR (CDCl₃, δ): 13.2 (CH₃), 18.8 (CH₃), 19.9 (CH₃), 26.4 (C5/

2.19−2.28 (m, 2H, H2), 2.36−2.40 (m, 2H, H7), 2.53−2.62 (m, 2H,

3

3+4

C6), 27.9 (C5/C6), 36.7 (C3), 44.7 (C4), 47.8 (C7), 49.8 (d, J_C,P

=

H4), 3.86 (pt,

J

= 1.9 Hz, 2H, C₅H₄), 4.25 (s, 5H, C₅H₅), 4.42

H,H

3+4

= 1.9 Hz, 2H, C₅H₄), 4.73−4.79 (m, 2H, H3). ¹³C{¹H}

NMR (CDCl₃, δ): 20.24 (C8), 20.26 (C8), 23.89 (C9/C10), 23.91

6.2 Hz, C1), 59.79 (C₅H₄), 59.83 (C₅H₄), 59.86 (C₅H₄), 59.89

(C₅H₄), 62.76 (C₅H₄), 62.79 (C₅H₄), 69.6 (C₅H₅), 85.9 (d, ²J_C,P= 6.8

Hz, C2), 117.64 (C_{C H}−O), 117.66 (C_{C H}−O), 117.68 (C_{C H}−O),

(pt,

J

H,H

(C9/C10), 27.40 (C9/C10), 27.41 (C9/C10), 33.76 (C7), 33.79

5

4

5

4

5

4

3

117.71 (C_{C H}−O). ³¹P{¹H} NMR (CDCl₃, δ): −9.8. HRMS (ESI-

(C7), 36.7 (d, J_C,P= 3.0 Hz, C4), 36.8 (d, J_C,P= 3.3 Hz, C4), 38.20

(C6), 38.22 (C6), 41.46 (C5), 45.19 (C2), 45.24 (C2), 45.27 (C2),

45.32 (C2), 47.7 (C1), 59.89 (C₅H₄), 59.91 (C₅H₄), 62.6 (C₅H₄),

69.5 (C₅H₅), 79.32 (C3), 79.34 (C3), 79.38 (C3), 79.40 (C3), 117.8−

117.9 (m, C_{C H}−O). ³¹P{¹H} NMR (CDCl₃, δ): −6.0. HRMS (ESI-

5

4

TOF, m/z): calcd for C₃₀H₃₅Fe₂O₄P 602.0967, found 602.0963 [M]⁺.

(1R)-α-Fenchyl Diferrocenyl Phosphate (9d). Ferrocenol (3; 1.00

g, 4.95 mmol), BuLi (2.0 mL, 5.0 mmol), and 8d (680 mg, 2.50

mmol) were reacted as described in the general procedure. Puriﬁcation

was realized by column chromatography (silica, 4 × 15 cm) using a

95/5 (v/v) dichloromethane/ethyl acetate mixture as the eluent.

Compound 9d was obtained as an orange solid.

5

4

TOF, m/z): calcd for C₃₀H₄₃FeO₄P 554.2243, found 554.2246 [M]⁺.

Cyclohexyl Diferrocenyl Phosphate (9a). Ferrocenol (3; 900 mg,

4.45 mmol), BuLi (1.8 mL, 4.5 mmol), and 8a (485 mg, 2.23 mmol)

were reacted as described in the general procedure. Puriﬁcation was

realized by column chromatography (silica, 4 × 15 cm) using a 95/5

(v/v) dichloromethane/ethyl acetate mixture as the eluent. Com-

pound 9a was obtained as an orange solid.

Yield: 935 mg (1.55 mmol, 63% based on 3). Anal. Calcd for

C₃₀H₃₅Fe₂O₄P (602.26): C, 59.83; H, 5.86. Found: C, 59.90; H, 6.00.

Mp: 129−132 °C. ¹H NMR (CDCl₃, δ): 0.90 (s, 3H, CH₃), 1.04−10.8

(m, 4H, CH₃, CH₂), 1.11 (s, 3H, CH₃), 1.16−1.21 (m, 1H, CH₂),

1.42−1.47 (m, 1H, CH₂), 1.50−1.54 (m, 1H, CH₂), 1.67−1.74 (m,

Yield: 771 mg (1.41 mmol, 63% based on 3). Anal. Calcd for

C₂₆H₂₉Fe₂O₄P (548.17): C, 56.97; H, 5.33. Found: C, 57.34; H, 5.43.

Mp: 90−93 °C. ¹H NMR (CDCl₃, δ): 1.31−1.40 (m, 2H, CH₂),

1.49−1.63 (m, 4H, CH₂), 1.71−1.81 (m, 2H, CH₂), 1.92−2.01 (m,

2H, CH₂), 3.87−3.92 (m, 4H, C₅H₄), 4.26 (s, 10H, C₅H₅), 4.37−4.43

(m, 4H, C₅H₄), 4.46−4.53 (m, 1H, H1). ¹³C{¹H} NMR (CDCl₃, δ):

23.5 (CH₂), 25.0 (CH₂), 33.2 (d, ³J_C,P= 2.9 Hz, C2/C6), 59.73−59.76

3

3H, CH₂, CH), 3.87−3.90 (m, 4H, C₅H₄), 4.04 (dd, J_C,P= 8.5 Hz,

J_H,H= 1.8 Hz, 1H, H2), 4.25 (s, 5H, C₅H₅), 4.25 (s, 5H, C₅H₅), 4.38−

4.46 (m, 4H, C₅H₄). ¹³C{¹H} NMR (CDCl₃, δ): 19.2 (CH₃), 20.8

(CH₃), 25.7 (C5/C6), 25.9 (C5/C6), 29.9 (CH₃), 39.6 (d, ³J_C,P= 2.7

3

Hz, C3), 40.9 (C7), 47.9 (C4), 49.3 (d, J_C,P= 5.1 Hz, C1), 59.91

(C₅H₄), 59.93 (C₅H₄), 59.94 (C₅H₄), 59.96 (C₅H₄), 59.98 (C₅H₄),

59.98 (C₅H₄), 62.71 (C₅H₄), 62.72 (C₅H₄), 62.75 (C₅H₄), 69.54

2

(m, C₅H₄), 62.73−62.74 (m, C₅H₄), 69.6 (C₅H₅), 79.0 (d, J_C,P= 6.6

2

(C₅H₅), 59.54 (C₅H₅), 92.3 (d, ²J_C,P= 7.4 Hz, C2), 117.77 (d, J_C,P

=

2

Hz, C1), 117.7 (d, J_C,P= 5.3 Hz, C_{C H}−O). ³¹P{¹H} NMR (CDCl₃,

4.9 Hz, C_{C H}−O), 117.81 (d, ²J_C,P= 4.7 Hz, C_{C H}−O). ³¹P{¹H} NMR

5

4

5

4

5

4

δ): −10.9. HRMS (ESI-TOF, m/z): calcd for C₂₆H₂₉Fe₂O₄P 548.0497,

(CDCl₃, δ): −9.8. HRMS (ESI-TOF, m/z): calcd for C₃₀H₃₅Fe₂O₄P

found 548.0490 [M]⁺.

602.0967, found 602.1005 [M]⁺.

Diferrocenyl (1R)-Menthyl Phosphate (9b). Ferrocenol (3; 1.10 g,

5.44 mmol), BuLi (2.2 mL, 5.5 mmol), and 8b (745 mg, 2.73 mmol)

were reacted as described in the general procedure. Puriﬁcation was

realized by column chromatography (silica, 4 × 15 cm) using a 5/95

(v/v) hexane/dichloromethane mixture as the eluent. Compound 9b

was obtained as an orange solid.

1,1′-Ferrocenediyl Tetracyclohexyl Bis(phosphate) (13a). With

1,1′-diacetoxyferrocene²⁹(712 mg, 2.36 mmol) as the starting

material, 1,1′-ferrocenediol (12) was prepared as described in the

standard procedure for the synthesis of ferrocenol^7,9,29,30(3) using

KOH/HCl (3 mL, 6 mmol) in 50 mL of ethanol. Ferrocenediol (12;

515 mg, 2.36), BuLi (1.9 mL, 4.75 mmol), and dicyclohexyl

chlorophosphate (8a; 1.40 g, 5.0 mmol) were then reacted as

described in the general procedure. Puriﬁcation was realized by

column chromatography (silica, 4 × 10 cm) using an 80/20 (v/v)

dichloromethane/ethyl acetate mixture as the eluent. Compound 13a

was obtained as an orange oil.

Yield: 1.222 g (2.02 mmol, 74% based on 3). Anal. Calcd for

C₃₀H₃₇Fe₂O₄P (604.28): C, 59.63; H, 6.17. Found: C, 59.88; H, 6.31.

1

3

Mp: 90−92 °C. H NMR (CDCl₃, δ): 0.80 (d, J_H,H= 6.9 Hz, 3H,

CH₃), 0.88−0.94 (m, 11H), 0.978−1.06 (m, 1H), 1.19, (m, 2H),

1.35−1.50 (m, 2H), 1.63−1.70 (m, 2H), 2.07−2.15 (m, 1H), 2.21−

2.28 (m, 1H), 3.86−3.92 (m, 4H, C₅H₄), 4.20−4.35 (m, 11H, C₅H₅,

H1), 4.37−4.44 (m, 4H). ¹³C{¹H} NMR (CDCl₃, δ): 15.7 (CH₃),

1

Yield: 980 mg (1.39 mmol, 59% based on 12). H NMR (CDCl₃,

δ): 1.23−1.38 (m, 12H, CH₂), 1.47−1.57 (m, 12H, CH₂), 1.70−1.77

3

3+4

20.9 (CH₃), 21.9 (CH₃), 22.8 (d, J_C,P= 27.0 Hz, CH₂), 25.4 (CH),

(m, 8H, CH₂), 1.89−1.98 (m, 8H, CH₂), 3.96 (pt,

J

= 1.9 Hz,

H,H

3

3+4

31.6 (CH), 33.9 (CH₂), 42.5 (CH₂), 48.4 (d, J_C,P= 7.3 Hz, CH),

4H, C₅H₄), 4.37−4.43 (m, 4H, H1), 4.44 (pt,

J

= 1.9 Hz, 4H,

H,H

C₅H₄). ¹³C{¹H} NMR (CDCl₃, δ): 23.5 (CH₂), 25.1 (CH₂), 33.21

59.8−59.9 (m, C₅H₄), 62.71 (C₅H₄), 62.74 (C₅H₄), 69.53 (C₅H₅),

2

3

69.56 (C₅H₅), 81.0 (d, J_C,P= 7.4 Hz, C1), 117.7 (d, J_C,P= 5.9 Hz,

(CH₂), 33.25 (CH₂), 33.27 (CH₂), 33.30 (CH₂), 61.2 (d, J_C,P= 3.7

−O). ³¹P{¹H} NMR (CDCl₃, δ): −10.7. HRMS (ESI-TOF, m/

Hz, C₅H₄), 64.6 (C₅H₄), 77.9 (d, ²J_C,P= 6.4 Hz, C1), 118.1 (²J_C,P= 4.8

Hz, C_{C H}−O). ³¹P{¹H} NMR (CDCl₃, δ): −6.9. HRMS (ESI-TOF,

C

C₅H₄

z): calcd for C₃₀H₃₇Fe₂O₄P 604.1124, found 604.1167 [M]⁺.

5

4

J

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

m/z): calcd for C₃₄H₅₂FeO₈P₂+ Na 729.2380, found 729.2333 [M +

Na]⁺.

CH), 31.4−31.5 (m, CH), 34.1−34.2 (m, CH₂), 43.2−43.5 (m, CH₂),

48.7−49.1 (m, CH), 54.6−54.8 (m, C₅H₃), 57.4 (OCH₃), 57.5 (d,

1

¹J_C,P= 216.9 Hz, C−P), 57.9 (OCH₃), 58.5 (d, J_C,P= 216.4 Hz,

1,1′-Ferrocenediyl Tetrakis((1R)-α-fenchyl) Bis(phosphate) (13b).

Ferrocenediol (12; 254 mg, 1.16 mmol), BuLi (0.95 mL, 2.38 mmol),

and dicyclohexyl chlorophosphate (8d; 1.00 g, 2.58 mmol) were

reacted as described in the general procedure. Puriﬁcation was realized

by column chromatography (silica, 4 × 10 cm) using a 95/5 (v/v)

dichloromethane/ethyl acetate mixture as the eluent. Compound 13b

was obtained as an orange oil.

C−P), 63.4 (d, J_C,P= 14.5 Hz, C₅H₃), 66.7 (d, J_C,P= 11.8 Hz, C₅H₃),

68.1 (d, J_C,P= 14.4 Hz, C₅H₃), 69.93 (C₅H₅), 69.96 (C₅H₅), 76.4 (d,

²J_C,P= 6.3 Hz, C1), 76.6 (d, ²J_C,P= 6.6 Hz, C1), 76.7 (d, ²J_C,P= 6.8 Hz,

2

C1), 76.9 (d, J_C,P= 7.6 Hz, C1), 127.9 (d, J_C,P= 9.0 Hz, C_{C H}−O),

5

3

129.0 (d, J_C,P= 10.9 Hz, C₅H₃). ³¹P{¹H} NMR (CDCl₃, δ): 20.6,

21.8. HRMS (ESI-TOF, m/z): calcd for C₃₁H₄₉FeO₄P 572.2713,

found 572.2733 [M]⁺.

2

1

Yield: 400 mg (0.43 mmol, 37% based on 12). H NMR (CDCl₃,

δ): 0.90−1.19 (m, 44H), 140−1.46 (m, 4H, CH₂), 1.49−1.51 (m, 4H,

CH₂), 1.70−1.71 (m, 12H, CH₂, CH), 3.95−4.00 (m, 8H, C₅H₄, H2),

4.47−4.50 (m, 4H, C₅H₄). ¹³C{¹H} NMR (CDCl₃, δ): 19.37 (CH₃),

19.39 (CH₃), 20.8 (CH₃), 21.0 (CH₃), 25.67 (C5/C6), 25.72 (C5/

C6), 25.94 (C5/C6), 25.97 (C5/C6), 29.91 (CH₃), 29.93 (CH₃),

39.5−39.6 (m, C3), 40.93 (C7), 40.96 (C7), 47.92 (C4), 47.94 (C4),

O,O-Bis((1S)-menthyl) 2-Methoxyferrocenyl Phosphonate (5c).

Ferrocenyl bis((1S)-menthyl) phosphate (4c; 100 mg, 0.18 mmol)

was reacted as described in procedure A. Compound 5c was obtained

as an orange oil as a mixture of two diastereomers.

1

Yield: 101 mg (0.18 mmol, 99% based on 4c). H NMR (CDCl₃,

δ): 0.41−0.57 (m, 3 H, CH₃), 0.78−0.94 (m, 19H, CH₂, CH₃), 0.98−

1.49 (m, 6H, CH₂, CH), 1.55−1.68 (m, 4H, CH₂, CH), 2.00−2.49 (m,

4H, CH₂, CH), 3.61−3.67 (3H, OCH₃), 3.96−4.30 (m, 10H, C₅H₅,

C₅H₃, H1). ¹³C{¹H} NMR (CDCl₃, δ): 15.4−15.8 (CH₃), 20.9−21.3

(CH₃), 21.98 (CH₃), 22.02 (CH₃), 22.6−22.8 (CH₂), 24.6 (CH), 25.1

(CH), 25.4 (CH), 31.4−31.5 (CH), 34.1−34.2 (CH₂), 43.2−43.5 (m,

C6), 48.7 (d, ³J_C,P= 7.4 Hz, C2), 48.8 (d, ³J_C,P= 7.4 Hz, C2), 48.9 (d,

³J_C,P= 6.4 Hz, C2), 49.1 (d, ³J_C,P= 7.4 Hz, C2), 54.7−54.9 (m, C₅H₃),

57.4 (OCH₃), 57.6 (d, ¹J_C,P= 216.7 Hz, C−P), 57.9 (OCH₃), 58.6 (d,

49.28 (C1), 49.32 (C1), 61.3 (d, ²J_C,P= 3.4 Hz, C₅H₄), 61.4 (d, ²J_C,P

=

3.8 Hz, C₅H₄), 64.59 (C₅H₄), 64.65 (C₅H₄), 91.1−91.2 (m, C2), 118.3

(d, ²J_C,P= 4.4 Hz, C_{C H}−O). ³¹P{¹H} NMR (CDCl₃, δ): −4.3. HRMS

5

4

(ESI-TOF, m/z): calcd for C₅₀H₇₆FeO₈P₂+ H 923.4439, found

923.4426 [M + H]⁺.

Anionic Phospho-Fries Rearrangement: General Procedure.

Procedure A (using Lithium Diisopropylamide (LDA) as the Base).

In a Schlenk tube hexane (3 mL) and diisopropylamine (0.05 mL, 0.36

mmol) were cooled to −30 °C. Afterward, BuLi (0.15 mL, 0.38 mmol)

was added dropwise, followed by addition of a diamine (tetramethy-

lethylenediamine: 0.05 mL, 0.33 mmol or (−)-sparteine (0.08 mL,

0.35 mmol)). The mixture was stirred for 10 min at −30 °C, and the

corresponding ferrocenyl phosphate 4a−f, 6a,d, 9a−c, or 13a,b was

added in a single portion. The obtained reaction mixture was warmed

to ambient temperature, and stirring was continued overnight. The

reaction mixture was quenched by adding dimethyl sulfate (0.15 mL,

1.58 mmol) and stirred at 50 °C for 1 h to complete methylation. All

volatiles were removed under reduced pressure. Puriﬁcation was

realized using column chromatography on silica using diﬀerent solvent

mixtures as eluents (see below).

¹J_C,P= 216.6 Hz, C−P), 63.4 (d, J_C,P= 13.6 Hz, C₅H₃), 66.7 (d, J_C,P

=

12.0 Hz, C₅H₃), 68.0 (d, J_C,P= 14.2 Hz, C₅H₃), 69.92 (C₅H₅), 69.94

(C₅H₅), 76.4 (d, ²J_C,P= 6.3 Hz, C1), 76.6 (d, ²J_C,P= 6.6 Hz, C1), 76.7

2

(d, J_C,P= 6.9 Hz, C1), 76.9 (d, J_C,P= 7.6 Hz, C1), 127.9 (d, J_C,P

=

9.1 Hz, C_{C H}−O), 129.0 (d, ²J_C,P= 10.9 Hz, C_{C H}−O). ³¹P{¹H} NMR

5

3

5

3

(CDCl₃, δ): 20.6 (¹J_P,C= 216.4 Hz), 21.8 (¹J_P,C= 216.9 Hz).

O,O-Bis((1S)-borneyl) 2-Methoxyferrocenyl Phosphonate (5d).

Bis((1S)-borneyl) ferrocenyl phosphate (4d; 100 mg, 0.18 mmol)

was reacted as described in procedure A. Compound 5d was obtained

as an orange oil as a mixture of two diastereomers.

1

Yield: 102 mg (0.18 mmol, 99% based on 4d). H NMR (CDCl₃,

δ): 0.79−0.93 (m, 18H, CH₃), 1.20−1.32 (m, 6H, CH₂), 1.60−1.67

(m, 2H, H4), 1.69−1.78 (m, 2H, CH₂), 1.99−2.13 (m, 2H, CH₂),

2.17−2.36 (m, 2H, CH₂), 3.65−3.66 (m, 3H, OCH₃), 3.98−4.00 (m,

1H, C₅H₃), 4.15−4.17 (m, 1H, C₅H₃), 4.20−4.24 (m, 1H, C₅H₃), 4.32

(s, 5H, C₅H₅), 4.59−4.73 (m, 2H, H2). ¹³C{¹H} NMR (CDCl₃, δ):

13.2−13.4 (CH₃), 18.80−18.82 (m, CH₃), 19.90−19.93 (CH₃), 26.5−

26.9 (C5/C6), 28.08−28.15 (C5/C6), 37.1−37.8 (m, C3), 44.86−

44.93 (C4), 47.4−47.5 (C7), 49.6−49.7 (C1), 54.7−54.9 (m, C₅H₃),

57.7 (OCH₃), 57.9 (OCH₃), 58.3 (d, ¹J_C,P= 218.1 Hz, C−P), 58.7 (d,

¹J_C,P= 217.9 Hz, C−P), 63.41 (d, J_C,P= 14.2 Hz, C₅H₃), 63.44 (d, J_C,P

= 13.9 Hz, C₅H₃), 66.95 (d, J_C,P= 12.8 Hz, C₅H₃), 67.03 (d, J_C,P= 13.2

Procedure B (using Lithium Tetramethylpiperidide (LTMP) as the

Base). In a Schlenk tube LTMP (56 mg, 0.38 mmol) was suspended in

3 mL of hexane and cooled to −30 °C. The addition of the diamine

and the respective ferrocenyl phosphate as well as the reaction

conditions and workup procedures were realized as described in

procedure A.

O,O-Dicyclohexyl 2-Methoxyferrocenyl Phosphonate (5a). Ferro-

cenyl dicyclohexyl phosphate (4a) (100 mg, 0.224 mmol) was reacted

as described in procedure A. Compound 5a was obtained as an orange

oil.

1

Yield: 100 mg (0.217 mmol, 97% based on 4a). H NMR (CDCl₃,

2

δ): 1.26−1.38 (m, 6H, CH₂), 1.17−1.62 (m, 6H, CH₂), 1.72−1.80 (m,

4H, CH₂), 1.87−1.98 (m, 4H, CH₂), 3.68 (s, 3H, OCH₃), 3.98−3.99

(m, 1H, C₅H₃), 4.16−4.17 (m, 1H, C₅H₃), 4.21−4.22 (m, 1H, C₅H₃),

4.31 (s, 5H, C₅H₅), 4.47−4.55 (m, 2H, H1). ¹³C{¹H} NMR (CDCl₃,

δ): 23.57 (CH₂), 23.59 (CH₂), 25.35 (CH₂), 25.36 (CH₂), 33.6 (d,

²J_C,P= 4.7 Hz, CH₂), 33.7 (d, ²J_C,P= 3.2 Hz, CH₂), 33.8 (d, ²J_C,P= 3.8

Hz, C₅H₃), 69.8 (C₅H₅), 69.9 (C₅H₅), 81.24 (d, J_C,P= 6.9 Hz, C2),

81.27 (d, ²J_C,P= 6.1 Hz, C2), 81.5 (d, ²J_C,P= 7.1 Hz, C2), 81.7 (d, ²J_C,P

2

= 6.4 Hz, C2), 128.4 (d, J_C,P= 9.9 Hz, C_{C H}−O), 128.6 (d, J_C,P

=

5

3

10.3 Hz, C_{C H}−O). ³¹P{¹H} NMR (CDCl₃, δ): 22.9, 23.2. HRMS

5

3

(ESI-TOF, m/z): calcd for C₃₁H₄₅FeO₄P 568.2400, found 568.2414

[M]⁺

2

Hz, CH₂), 33.9 (d, J_C,P= 3.2 Hz, CH₂), 55.0 (d, J_C,P= 11.4 Hz,

(R_p)-O,O-Bis((1R)-α-fenchyl) 2-Methoxyferrocenyl Phosphonate

(5e). Ferrocenyl bis((1R)-α-fenchyl) phosphate (4e; 100 mg, 0.18

mmol) was reacted as described in procedure B. Compound 5e was

obtained as an orange solid. The spectroscopic data correspond to the

single diastereomer, which was obtained after crystallization (de =

0.80).

C₅H₃), 58.0 (OCH₃), 59.1 (d, ¹J_C,P= 216.6 Hz, C−P), 63.4 (d, J_C,P

=

14.0 Hz, C₅H₃), 67.1 (d, J_C,P= 12.8 Hz, C₅H₃), 69.9 (C₅H₅), 74.76 (d,

²J_C,P= 6.5 Hz, C1), 74.82 (d, ²J_C,P= 7.2 Hz, C1), 128.4 (d, ²J_C,P= 10.4

Hz, C_{C H}−O). ³¹P{¹H} NMR (CDCl₃, δ): 21.2 (¹J_P,C= 216.8 Hz).

5

3

HRMS (ESI-TOF, m/z): calcd for C₂₃H₃₃FeO₄P + H 461.1539, found

461.1530 [M + H]⁺.

Yield: 90 mg (0.16 mmol, 88% based on 4e). Mp: 186−188 °C. ¹H

NMR (CDCl₃, δ): 0.87 (s, 3H, CH₃), 0.88 (s, 3H, CH₃), 0.92 (s, 3H,

CH₃), 0.96−1.06 (m, 5H), 1.10−1.18 (m, 8H), 1.39−1.52 (m, 4H),

1.64−1.87 (m, 6H), 3.68 (s, 3H, OCH₃), 3.99−4.06 (m, 3H, H2,

C₅H₃), 4.14−4.18 (m, 1H, C₅H₃), 4.19−4.23 (m, 1H, C₅H₃), 4.35 (s,

5H, C₅H₅). ¹³C{¹H} NMR (CDCl₃, δ): 19.2 (CH₃), 19.6 (CH₃), 21.1

(CH₃), 21.4 (CH₃), 25.8−26.2 (m, C5/C6), 29.7 (CH₃), 29.8 (CH₃),

39.1 (d, ³J_C,P= 2.2 Hz, C7), 39.7 (d, ³J_C,P= 2.2 Hz, C7), 41.07 (CH₂),

O,O-Bis((1R)-menthyl) 2-Methoxyferrocenyl Phosphonate (5b).

Ferrocenyl bis((1R)-menthyl) phosphate (4b; 100 mg, 0.18 mmol)

was reacted as described in procedure A. Compound 5b was obtained

as an orange oil as a mixture of two diastereomers.

1

Yield: 101 mg (0.18 mmol, 99% based on 4b). H NMR (CDCl₃,

δ): 0.41−1.06 (m, 22H), 1.12−1.50 (m, 6H), 1.57−1.71 (m, 4H),

2.02−2.48 (m, 4H), 3.62−3.68 (m, 3H, OCH₃), 3.92−4.32 (m, 10H).

¹³C{¹H} NMR (CDCl₃, δ): 15.4−15.8 (m, CH₃), 21.1−21.3 (m,

CH₃), 22.01−22.04 (m, CH₃), 22.5−22.7 (m, CH₂), 24.6−25.4 (m,

3

41.09 (CH₂), 48.0 (C4), 48.1 (C4), 49.25 (d, J_C,P= 4.8 Hz, C1),

3

49.34 (d, J_C,P= 4.4 Hz, C1), 54.8 (d, J_C,P= 11.8 Hz, C₅H₃), 57.8

K

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

1

(OCH₃), 58.2 (d, J_C,P= 216.6 Hz, C−P), 63.6 (d, J_C,P= 13.6 Hz,

mmol), TMEDA (0.07 mL, 0.46 mmol), and 2a (375 mg, 1.7 mmol)

were reacted as described in the general procedure. Puriﬁcation was

realized by column chromatography (silica, 2 × 8 cm) using an 80/20

(v/v) dichloromethane/ethyl acetate mixture (R_f= 0.43) as the eluent.

Compound 6b was obtained as and orange oil.

C₅H₃), 67.2 (d, J_C,P= 12.1 Hz, C₅H₃), 69.8 (C₅H₅), 87.8 (d, ²J_C,P= 6.4

2

Hz, C2), 88.0 (d, J_C,P= 6.7 Hz, C2), 128.8 (d, J_C,P= 10.3 Hz,

C_{C H}−O). ³¹P{¹H} NMR (CDCl₃, δ): 22.4. HRMS (ESI-TOF, m/z):

5

3

calcd for C₃₁H₄₅FeO₄P 568.2400, found 568.2433 [M]⁺.

1

Yield: 150 mg (0.188 mmol, 81% based on 4a). H NMR (CDCl₃,

Crystal data for 5e: C₃₁H₄₅FeO₄P, M_r= 568.49, orthorhombic,

P2₁2₁2₁, λ = 0.71073 Å, a = 7.7485(2) Å, b = 10.6896(3) Å, c =

34.4462(10) Å, V = 2853.12(14) Å³, Z = 4, ρ_calcd= 1.323 Mg m⁻³, μ =

0.619 mm⁻¹, T = 110.00(10) K, θ range 2.88−26.00°, 25582

reﬂections collected, 5602 independent reﬂections (R_int= 0.0363),

R1 = 0.0269, wR2 = 0.0580 (I > 2σ(I)), absolute structure parameter²⁸

0.000(10).

O,O-Bis((1S)-isopinocampheyl) 2-Methoxyferrocenyl Phospho-

nate (5f). Ferrocenyl bis((1S)-isopinocampheyl) phosphate (4f; 100

mg, 0.18 mmol) was reacted as described in procedure A. Compound

5f was obtained as an orange oil as a mixture of two diastereomers.

Yield: 85 mg (0.15 mmol, 80% based on 4f). ¹H NMR (CDCl₃, δ):

0.90−0.93 (m, 6H), 1.05−1.21 (m, 14H), 1.77−1.83 (m, 2H), 1.89−

2.08 (m, 4H, 2.15−2.26 (m, 2H), 2.33−2.39 (m, 2H), 2.46−2.60 (m,

2H), 3.67/3.68 (s, 3H, OCH₃), 3.99−4.00 (m, 1H, C₅H₃), 4.16−4.18

(m, 1H, C₅H₃), 4.22−4.27 (m, 1H, C₅H₃), 4.320/4.321 (s, 5H, C₅H₅),

4.70−4.85 (m, 2H, H1). ¹³C{¹H} NMR (CDCl₃, δ): 19.95 (CH₃),

20.02 (CH₃), 23.78 (CH₃), 23.81 (CH₃), 23.83 (CH₃), 27.43 (CH₃),

27.47 (CH₃), 27.49 (CH₃), 27.50 (CH₃), 33.6 (CH₂), 33.7 (CH₂),

δ): 1.28−1.41 (m, 12H, CH₂), 1.45−1.65 (m, 12H, CH₂), 1.67−1.81

(m, 8H, CH₂), 1.83−1.89 (m, 1H, CH₂), 1.89−2.06 (m, 7H, CH₂),

4.02−4.05 (m, 1H, C₅H₃), 4.22−4.25 (m, 1H, C₅H₃), 4.36 (s, 5H,

C₅H₅), 4.40−4.47 (m, 1H, H1), 4.48−4.54 (m, 1H, H1), 4.78−4.82

(m, 1H, C₅H₃). ¹³C{¹H} NMR (CDCl₃, δ): 23.45 (CH₂), 23.49

(CH₂), 23.60 (CH₂), 23.62 (CH₂), 23.7 (CH₂), 25.11 (CH₂), 25.14

3

(CH₂), 25.30 (CH₂), 25.34 (CH₂), 33.2 (d, J_C,P= 4.7 Hz, CH₂),

33.27 (d, ³J_C,P= 4.5 Hz, CH₂), 33.31 (d, ³J_C,P= 4.2 Hz, CH₂), 33.5 (d,

³J_C,P= 4.4 Hz, CH₂), 33.8 (d, ³J_C,P= 3.7 Hz, CH₂), 33.9 (d, ³J_C,P= 3.9

1

3

Hz, CH₂), 59.7 (dd, J_C,P= 217.0 Hz, J_C,P= 8.6 Hz, C−P), 62.0 (d,

J_C,P= 11.3, C₅H₃), 64.5 (d, J_C,P= 13.8, C₅H₃), 67.4 (d, J_C,P= 13.1,

C₅H₃), 71.2 (C₅H₅), 74.9 (d, J_C,P= 5.9 Hz, C1), 75.1 (d, J_C,P= 6.6

2

Hz, C1), 77.91 (d, J_C,P= 6.4 Hz, C1), 77.94 (d, J_C,P= 6.3 Hz, C1),

118.5 (dd, J_C,P= 8.9 Hz, J_C,P= 5.0 Hz, C_{C H}−O). ³¹P{¹H} NMR

2

5

3

(CDCl₃, δ): −7.4 (PO₄), 19.8 (PO₃). HRMS (ESI-TOF, m/z): calcd

for C₃₄H₅₂FeO₇P₂+ Na 713.2340, found 713.2373 [M + Na]⁺.

2-(O,O-Dicyclohexylphosphonato)ferrocenyl Bis((1R)-α-fenchyl)

Phosphate (6c). Dicyclohexyl ferrocenyl phosphate (4a; 100 mg,

0.22 mmol), diisopropylamine (0.07 mL, 0.50 mmol), BuLi (0.2 mL,

0.50 mmol), TMEDA (0.07 mL, 0.46 mmol), and 2e (370 mg, 0.95

mmol) were reacted as described in the general procedure. Puriﬁcation

was realized by column chromatography (silica, 2 × 12 cm) using an

80/20 (v/v) dichloromethane/ethyl acetate mixture (R_f= 0.45) as the

eluent. Compound 6c was obtained as an orange oil in a mixture of

diastereomers (de = 0.10).

3

33.8 (CH₂), 37.1 (d, J_C,P= 3.1 Hz, CH₂), 27.3 (d, J_C,P= 2.87 Hz,

3

CH₂), 37.4 (d, J_C,P= 2.5 Hz, CH₂), 37.5 (d, J_C,P= 2.2 Hz, CH₂),

38.15 (C6), 38.17 (C6), 38.20 (C6), 41.52 (C5), 41.53 (C5), 41.56

(C5), 41.60 (C5), 45.5−45.8 (m, C2), 47.7 (C1), 47.8 (C1), 55.03 (d,

J_C,P= 11.3 Hz, C₅H₃), 55.09 (d, J_C,P= 11.3 Hz, C₅H₃), 57.96 (OCH₃),

57.99 (OCH₃), 58.5 (d, ¹J_C,P= 215.8 Hz, C−P), 58.7 (d, ¹J_C,P= 215.7

Hz, C−P), 63.4 (d, J_C,P= 13.9 Hz, C₅H₃), 63.4 (d, J_C,P= 13.9 Hz,

C₅H₃), 67.2 (d, J_C,P= 12.8 Hz, C₅H₃), 67.4 (d, J_C,P= 12.9 Hz, C₅H₃),

70.0 (C₅H₅), 75.9 (d, ²J_C,P= 6.8 Hz, C3), 76.0 (d, ²J_C,P= 7.3 Hz, C3),

76.2 (d, ²J_C,P= 6.8 Hz, C3), 76.3 (d, ²J_C,P= 7.4 Hz, C3), 128.4 (d, ²J_C,P

1

Yield: 150 mg (0.188 mmol, 81% based on 4a). H NMR (CDCl₃,

δ): 0.84−1.58 (m, 40H, C₆H₁₁, C₆H₁₇), 1.67−1.77 (m, 8H, C₆H₁₁,

C₆H₁₇), 1.92−2.03 (m, 4H, C₆H₁₁), 3.98−4.13 (m, 3H, C₅H₃,

C₁₀H₁₇), 4.18−4.23 (m, 1H, C₅H₃), 4.36 (s, 5H, C₅H₅), 4.44−4.57 (m,

1H, C₆H₁₁), 4.89−4.98 (m, 1H, C₅H₃). ¹³C{¹H} NMR (CDCl₃, δ):

19.4−19.5 (m, CH₃), 20.7−21.1 (m, CH₃), 23.76−23.84 (m, Cy_CH2),

25.7−26.0 (m, C5/C6), 29.8−30.0 (m, CH₃), 33.8−34.0 (m, Cy_CH2),

39.5−39.7 (m, C3), 40.9−41.0 (m, C7), 47.9−48.0 (C4), 49.2−49.4

= 10.1 Hz, C−O), 128.6 (d, J_C,P= 10.2 Hz, C−O). ³¹P{¹H} NMR

2

(CDCl₃, δ): 21.24, 21.28. HRMS (ESI-TOF, m/z): calcd for

C₃₁H₄₅FeO₄P 568.24000, found 568.2453 [M]⁺.

O,O-Dicyclohexyl 2-(Diphenylthiophosphinato)ferrocenyl Phos-

phonate (6a). Dicyclohexyl ferrocenyl phosphate (4a; 100 mg, 0.22

mmol), diisopropylamine (0.07 mL, 0.50 mmol), BuLi (0.2 mL, 0.50

mmol), TMEDA (0.07 mL, 0.46 mmol), ClPPh₂(0.17 mL, 0.93

mmol), and sulfur (60 mg, 1.9 mmol) were reacted as described in the

general procedure. The obtained reaction mixture was ﬁltered through

a pad of Celite using hexane to remove the excess of sulfur.

Compound 6a was puriﬁed by column chromatography (silica, 2 × 8

cm column size) using a 90/10 (v/v) dichloromethane/ethyl acetate

mixture as the eluent and obtained as an orange oil.

(m, C1), 59.7 (d, ¹J_C,P= 218.7 Hz, ³J_C,P= 8.4 Hz, C−P), 62.5 (d, J_C,P

=

10.6 Hz, C₅H₃), 62.7 (d, J_C,P= 10.8 Hz, C₅H₃), 64.30 (d, J_C,P= 13.6

Hz, C₅H₃), 64.36 (d, J_C,P= 13.7 Hz, C₅H₃), 67.5 (d, J_C,P= 12.8 Hz,

C₅H₃), 67.6 (d, J_C,P= 12.4 Hz, C₅H₃), 71.21 (C₅H₅), 71.23 (C₅H₅),

74.9 (d, ²J_C,P= 6.4 Hz, Cy_C1), 75.05 (d, ²J_C,P= 5.8 Hz, Cy_C1), 75.18 (d,

²J_C,P= 6.7 Hz, Cy_C1), 91.3−91.5 (m, Fn_C1), 119.0−119.2 (m,

C_{C H}−O). ³¹P{¹H} NMR (CDCl₃, δ): −4.4 (PO₄), −3.7 (PO₄), 19.88

5

3

1

(PO₃), 19.93 (PO₃). HRMS (ESI-TOF, m/z): calcd for C₄₂H₆₄FeO₇P₂

Yield: 65 mg (0.098 mmol, 44% based on 4a). H NMR (CDCl₃,

+ H 799.3550, found 799.3496 [M + H]⁺.

δ): 1.19−1.31 (m, 6H, CH₂), 1.41−1.54 (m, 6H, CH₂), 1.63−1.78 (m,

4H, CH₂), 1.82−1.88 (m, 1H, CH₂), 1.88−2.02 (m, 3H, CH₂), 3.96

(ddd, J_H,H= J_H,H= J_H,P= 2.8 Hz, 1H, C₅H₃), 4.19−4.23 (m, 6H, C₅H₅,

C₅H₃), 4.45−4.54 (m, 2H, H1), 4.60−4.62 (m, 1H, C₅H₃), 7.39−7.43

(m, 2H, Ph), 7.45−7.49 (m, 1H, Ph), 7.50−7.56 (m, 3H, Ph), 7.96−

8.00 (m, 2H, Ph), 8.12−8.17 (m, 2H, Ph). ¹³C{¹H} NMR (CDCl₃, δ):

23.55 (CH₂), 23.64 (CH₂), 23.70 (CH₂), 23.72 (CH₂), 25.21 (CH₂),

25.24 (CH₂), 33.7 (d, J_C,P= 4.5 Hz, CH₂), 33.9−34.0 (m, CH₂), 59.8

(dd, ¹J_C,P= 217.1 Hz, ³J_C,P= 5.4 Hz, C_{C H}P), 62.8 (dd, J_C,P= 10.3 Hz,

Bis((1R)-fenchyl) (2-(O,O-Bis((1R)-α-fenchyl)phosphonato)-

ferrocenyl) Phosphate (6d). Ferrocenyl bis((1R)-α-fenchyl) phos-

phate (4e; 300 mg, 0.54 mmol), LTMP (210 mg, 1.41 mmol),

TMEDA (0.15 mL, 1.0 mmol), and 2e (420 mg, 1.08 mmol) were

reacted as described in the general procedure. Compound 6e was

puriﬁed using column chromatography (silica, 2 × 12 cm column size)

using a 96/4 (v/v) dichloromethane/ethyl acetate mixture as the

eluent. Compound 6d was obtained as an orange oil in a mixture of

two diastereomers (de = 0.95).³¹

5

3

1

J_C,P= 5.5 Hz, C₅H₃), 64.6 (d, J_C,P= 13.9 Hz, C₅H₃), 66.9 (d, J_C,P

=

Yield: 422 mg (0.465 mmol, 86% based on 4e). H NMR (CDCl₃,

2

12.8 Hz, C₅H₃), 71.3 (C₅H₅), 75.1 (d, J_C,P= 6.3 Hz, C1), 75.2 (d,

δ): 0.73 (s, 3H, CH₃), 0.88−1.27 (m, 41H, C₁₀H₁₇), 1.34−1.58 (m,

8H, C₁₀H₁₇), 1.61−1.81 (m, 11H, C₁₀H₁₇), 1.86−1.90 (m, 1H,

C₁₀H₁₇), 3.89 (dd, ³J_H,P= 10.2 Hz, J_H,H= 1.5 Hz, 1H, H2), 4.04−4.10

²J_C,P= 6.5 Hz, C1), 118.8 (dd, ²J_C,P= 9.2 Hz, ²J_C,P= 6.8 Hz, C_{C H}−O),

5

3

128.4 (d, J_C,P= 5.5 Hz, Ph), 128.5 (d, J_C,P= 5.5 Hz, Ph), 131.5 (d, J_C,P

= 11.8 Hz, Ph), 131.8 (d, J_C,P= 11.9 Hz, Ph), 131.9 (d, J_C,P= 3.0 Hz,

3

(m, 3H, H2, C₅H₃), 4.14 (dd, J_H,P= 8.7 Hz, J_H,H= 1.5 Hz, 1H, H2),

3

1

4.23 (dd, J_H,P= 9.5 Hz, J_H,H= 1.4 Hz, 1H, H2), 4.41 (s, 5H, C₅H₅),

Ph), 132.1 (d, J_C,P= 3.0 Hz, Ph), 134.0 (d, J_C,P= 111.1 Hz, C_Ph−P),

4.97−4.98 (m, 1H, C₅H₃). ¹³C{¹H} NMR (CDCl₃, δ): 19.2 (CH₃),

19.66 (CH₃), 19.67 (CH₃), 19.9 (CH₃), 20.9 (CH₃), 21.1 (CH₃), 21.5

(CH₃), 22.0 (CH₃), 25.77 (C5/C6), 25.81 (C5/C6), 25.89 (C5/C6),

(C5/C6), 26.00 (C5/C6), 26.03 (C5/C6), 26.13 (C5/C6), 26.14

(C5/C6), 29.7 (CH₃), 29.86 (CH₃), 29.89 (CH₃), 30.1 (CH₃), 39.3

134.4 (d, J_C,P= 111.4 Hz, C_Ph−P.) ³¹P{¹H} NMR (CDCl₃, δ): 20.4

1

(PO₃), 80.3 (PS). HRMS (ESI-TOF, m/z): calcd for

C₃₄H₄₀FeO₄P₂S + H 663.1545, found 663.1477 [M + H]⁺.

Dicyclohexyl 2-(O,O-Dicyclohexylphosphonato)ferrocenyl Phos-

phate (6b). Dicyclohexyl ferrocenyl phosphate (4a; 100 mg, 0.22

mmol), diisopropylamine (0.07 mL, 0.50 mmol), BuLi (0.2 mL, 0.50

(d, ³J_C,P= 1.4 Hz, C3), 39.55 (d, ³J_C,P= 2.5 Hz, C3), 39.64 (d, ³J_C,P

=

L

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

3

2.6 Hz, C3), 39.8 (d, J_C,P= 1.2 Hz, C3), 40.8 (C7), 41.0 (C7), 41.2

²J_C,P= 6.5 Hz, C2), 88.8 (d, ²J_C,P= 5.4 Hz, C2), 89.0 (d, ²J_C,P= 7.3 Hz,

(C7), 47.96 (C4), 47.98 (C4), 48.05 (C4), 48.2 (C4), 49.1 (d, ³J_C,P

=

2

C2), 90.9 (d, J_C,P= 8.9 Hz, C2), 130.0 (dd, J_C,P= 13.8 Hz, J_C,P

=

5.6 Hz, C1), 49.4 (d, ³J_C,P= 5.1 Hz, C1), 49.5 (d, ³J_C,P= 5.2 Hz, C1),

59.1 (dd, ¹J_C,P= 217.1 Hz, ³J_C,P= 10.0 Hz, C−P), 62.0 (d, J_C,P= 10.8,

C₅H₃), 64.7 (d, J_C,P= 12.8, C₅H₃), 66.8 (d, J_C,P= 10.3, C₅H₃), 71.2

(C₅H₅), 87.6 (d, ²J_C,P= 5.5 Hz, C2_PO), 88.3 (d, ²J_C,P= 7.8 Hz, C2_PO),

10.5 Hz, C−OH). ³¹P{¹H} NMR (CDCl₃, δ): 21.3 (d, ³J_P,P= 3.7 Hz),

3

25.8 (d, J_P,P= 3.7 Hz).

1,1′-Bis(O,O-bis((1R)-α-fenchyl)phosphonato)-2-methoxyferro-

cene (7c). Bis((1R)-α-fenchyl) 2-(O,O-bis((1R)-α-fenchyl)-

phosphonato)ferrocenyl phosphate (6d; 45 mg, 0.05 mmol), LTMP

(24 mg, 0.16 mmol), TMEDA (0,03 mL, 0.20 mmol), and Me₂SO₄

(0.1 mL, 1.05 mmol) were reacted as described in the general

procedure. Puriﬁcation was realized using column chromatography

(silica, 2 × 12 cm column size) using a 85/15 (v/v) dichloromethane/

ethyl acetate mixture as the eluent. Compound 7c was obtained as an

orange oil.

3

91.1 (d, ²J_C,P= 6.5 Hz, C2_PO4), 91.7 (d, ²J_C,P= 6.6 Hz, C2_PO), 120.69

4

(C_{C H}−O), 120.73 (C_{C H}−O), 120.78 (C_{C H}−O), 120.81

(C_{C H}−O). ³¹P{¹H} NMR (CDCl₃, δ): −3.5 (d, J_P,P= 0.9 Hz,

PO₄), 19.6 (d, J_P,P= 1.9 Hz, PO₃; dd J_P,C= 216.9 Hz, 1.9 Hz).

HRMS (ESI-TOF, m/z): calcd for C₅₀H₇₆FeO₇P₂+ H 907.4489,

found 907.4409 [M + H]⁺.

5

3

5

3

5

3

4

5

3

4

1

Yield: 12 mg (0.013 mmol, 26% based on 6d). H NMR (CDCl₃,

Crystal data for 6d: C_50.25H_76.5Cl_0.5FeO₇P₂, M_r= 928.12,

δ): 0.65 (s, 3H, CH₃), 0.87−1.26 (m, 37H, C₁₀H₁₇), 1.38−1.57 (m,

8H, C₁₀H₁₇), 1.59−1.87 (m, 12H, C₁₀H₁₇), 3.74−3.76 (m, 4H, OCH₃,

H2), 4.00−4.05 (m, 2H, H2), 4.18 (dd, J_H,P= 9.73 Hz, J_H,H= 1.5 Hz,

H2), 4.27−4.30 (m, 2H, C₅H₃), 4.43−4.45 (m, 1H, C₅H₄), 4.46−4.47

(m, 1H, C₅H₃), 4.66−4.68 (m, 1H, C₅H₄), 4.70−4.72 (m, 1H, C₅H₄),

4.73−4.75 (m, 1H, C₅H₄). ¹³C{¹H} NMR (CDCl₃, δ): 19.15 (CH₃),

19.23 (CH₃), 19.6 (CH₃), 19.7 (CH₃), 21.1 (CH₃), 21.45 (CH₃),

21.48 (CH₃), 21.7 (CH₃), 25.77 (C5/C6), 25.84 (C5/C6), 25.95

(C5/C6), 26.0 (C5/C6), 26.1 (C5/C6), 26.2 (C5/C6), 29.65 (CH₃),

29.67 (CH₃), 29.69 (CH₃), 29.74 (CH₃), 29.80 (CH₃), 39.10 (C3),

39.11 (C3), 39.15 (C3), 39.16 (C3), 39.70 (C3), 39.71 (C3), 39.72

(C3), 39.73 (C3), 40.8 (C7), 41.0 (C7), 41.1 (C7), 47.94 (C4), 47.98

monoclinic, C2, λ = 0.71073 Å, a = 43.1922(8) Å, b = 8.5461(2) Å,

c = 26.5582(5) Å, β = 90.458(2)°, V = 9803.0(3) Å³, Z = 8, ρ_calcd

=

1.258 Mg m⁻³, μ = 0.449 mm⁻¹, T = 110.00(10) K, θ range 2.875−

25.50°, 41406 reﬂections collected, 16504 independent reﬂections

(R_int= 0.0229), R1 = 0.0333, wR2 = 0.0807 (I > 2σ(I)), absolute

structure parameter²⁸0.005(4).

1,3-Bis(O,O-dicyclohexylphosphonato)-2-methoxyferrocene (7a).

Dicyclohexyl 2-(O,O-dicyclohexylphosphonato)ferrocenyl phosphate

(6a; 68 mg, 0.10 mmol), diisopropylamine (0.03 mL, 0.20 mmol),

BuLi (0.08 mL, 0.20 mmol), TMEDA (0.03 mL, 0.20 mmol), and

Me₂SO₄(0.1 mL, 0.8 mmol) were reacted as described in the general

procedure. Compound 7a was puriﬁed using column chromatography

(silica, 2 × 10 cm column size) using a 95/5 (v/v) ethyl acetate/

methanol mixture as the eluent. Compound 7a was obtained as an

orange oil.

3

(C4), 48.03 (C4), 48.08 (C4), 49.1 (d, J_C,P= 5.4 Hz, C1), 49.2 (d,

³J_C,P= 5.1 Hz, C1), 49.3 (d, ³J_C,P= 4.7 Hz, C1), 49.4 (d, ³J_C,P= 5.2 Hz,

1

C1), 56.9 (d, J_C,P= 11.4 Hz, C₅H₃), 58.0 (OCH₃), 58.7 (d, J_C,P

=

Yield: 28 mg (0.04 mmol, 41% based on 6a). ¹H NMR (CDCl₃, δ):

1.24−1.34 (m, 12H, CH₂), 1.42−1.56 (m, 12H, CH₂), 1.64−1.80 (m,

8H, CH₂), 1.81−2.02 (m, 8H, CH₂), 3.91 (m, 3H, OCH₃), 4.35−4.22

(m, 2H, C₅H₂), 4.43−4.57 (m, 9H, C₅H₅, H1). ¹³C{¹H} NMR

(CDCl₃, δ): 23.55 (CH₂), 23.57 (CH₂), 25.23 (CH₂), 33.50 (CH₂),

33.52 (CH₂), 33.53 (CH₂), 33.65 (CH₂), 33.77 (CH₂), 33.78 (CH₂),

215.1 Hz, C_{C H}P), 66.0 (d, J_C,P= 13.2 Hz, C₅H₃), 68.0 (d, J_C,P= 11.9

5

3

1

Hz, C₅H₃), 68.4 (d, J_C,P= 216.8 Hz, C_C5H4−P), 71.8 (d, J_C,P= 13.1

Hz, C₅H₄), 73.7 (d, J_C,P= 13.4 Hz, C₅H₄), 74.6 (d, J_C,P= 16.4 Hz,

2

C₅H₄), 75.0 (d, J_C,P= 14.0 Hz, C₅H₄), 88.0 (d, J_C,P= 6.3 Hz, C2),

88.1 (d, ²J_C,P= 6.5 Hz, C2), 88.3 (d, ²J_C,P= 5.9 Hz, C2), 88.5 (d, ²J_C,P

2

= 7.8 Hz, C2), 129.8 (d, J_C,P= 10.4 Hz, C_{C H}−O). ³¹P{¹H} NMR

5

3

1

33.79 (CH₂), 33.86 (CH₂), 63.7 (CH₃), 64.1 (dd, J_C,P= 212.1 Hz,

(CDCl₃, δ): 21.3 (C₅H₃), 23.8 (C₅H₄).

³J_C,P= 10.6 Hz, C−P), 69.3 (pt, ²⁺³J_C,P= 13.6 Hz, C₅H₂), 72.1 (C₅H₅),

75.14 (C1), 75.19 (C1), 75.21 (C1), 75.27 (C1), 128.1 (t, ²J_C,P= 10.9

Hz, C_{C H}−O). ³¹P{¹H} NMR (CDCl₃, δ): 19.8. HRMS (ESI-TOF,

1′-(Bis((1R)-α-fenchyl)phosphato)-2-methoxyferrocenyl O,O-Bis-

((1R)-α-fenchyl) Phosphonate (14b). 1,1′-Ferrocenediyl tetrakis-

((1R)-α-fenchyl) bis(phosphate) (13b; 120 mg, 0.13 mmol), LTMP

(115 mg, 0.78 mmol), TMEDA (0.12 mL, 0.78 mmol), and Me₂SO₄

(0.22 mL, 2.3 mmol) were reacted as described in the general

procedure. Puriﬁcation was realized by column chromatography (silica,

2 × 12 cm column size) using a 90/10 (v/v) dichloromethane/ethyl

acetate mixture as the eluent. Compound 14b was obtained as an

orange oil as a mixture of both diastereomers (de = 0.84).

5

2

m/z): calcd for C₃₅H₅₄FeO₇P₂+ Na 727.2587, found 727.2589 [M +

Na]⁺.

1,3-Bis(O,O-bis((1R)-α-fenchyl)phosphonato)-2-hydroxyferrocene

(7b). Bis((1R)-α-fenchyl) 2-(O,O-bis((1R)-α-fenchylphosphonato)-

ferrocenyl phosphate (6d; 100 mg, 0.11 mmol), diisopropylamine

(0.05 mL, 0.36 mmol), BuLi (0.15 mL, 0.38 mmol), TMEDA (0.06

mL, 0.4 mmol), and Me₂SO₄(0.2 mL, 2.1 mmol) were reacted as

described in the general procedure. Compound 7b was puriﬁed using

column chromatography (silica, 2 × 10 cm column size) using a 70/30

(v/v) dichloromethane/ethyl acetate mixture as the eluent. Com-

pound 7b was obtained as an orange oil.

Yield: 22 mg (0.024 mmol, 18% based on 13b). ¹H NMR (CDCl₃,

δ): 0.85−1.28 (m, 44H), 1.44−1.52 (m, 8H, CH₂), 1.66−1.75 (m,

12H, CH₂, CH), 3.74 (s, OCH₃), 3.95−4.04 (m, 4H, H2), 4.13−4.14

(m, 2H, C₅H_X), 4.21−4.23 (m, 2H, C₅H_X), 4.28−4.29 (m, 1H, C₅H_X),

4.49−4.50 (m, 1H, C₅H_X), 4.58−4.59 (m, 1H, C₅H_X). ¹³C{¹H} NMR

(CDCl₃, δ): 19.18 (CH₃), 19.37 (CH₃), 19.41 (CH₃), 19.61 (CH₃),

20.8 (CH₃), 21.0 (CH₃), 21.1 (CH₃), 21.4, 25.6−26.2 (m, C5/C6),

1

Yield: 99 mg (0.109 mmol, 99% based on 6d). H NMR (CDCl₃,

δ): 0.79 (s, 3H, CH₃), 0.94−1.28 (m, 41H), 1.30−1.35 (m, 1H, CH₂),

3

29.7−29.8 (m, CH₃), 39.1 (d, J_C,P= 2.2 Hz, C3), 39.5 (d, J_C,P= 2.4

1.39−1.56 (m, 6H, CH₂), 1.59−1.61 (m, 1H, CH₂), 1.65−1.89 (m,

3

Hz, C3), 39.6 (d, J_C,P= 2.4 Hz, C3), 39.7 (d, J_C,P= 2.2 Hz, C3),

40.9−41.1 (m, C7), 47.9−48.1 (m, C4), 49.2−49.3 (m, C1), 57.5 (d,

J_C,P= 11.7 Hz, C₅H₃), 57.9 (OCH₃), 58.4 (d, ¹J_C,P= 218.4 Hz, C−P),

60.7 (d, J_C,P= 3.5 Hz, C₅H₄), 62.0 (d, J_C,P= 4.1 Hz, C₅H₄), 64.8

11H), 1.91−1.98 (m, 1H, CH₂), 3.50 (dd, J_H,P= 9.5 Hz, J_H,H= 1.4

3

Hz, 1 H, H2), 3.87 (dd, J_H,P= 9.7 Hz, J_H,H= 1.5 Hz, 1H, H2), 4.12

(dd, J = 5.0 Hz, J = 2.6 Hz, 1H, C₅H₂), 4.21 (dd, ³J_H,P= 10.2 Hz, J_H,H

=

1.3 Hz, 1H, H2), 4.30 (dd, ³J_H,P= 9.0 Hz, J_H,H= 1.4 Hz, 1H, H2), 4.42

(dd, J = 4.8 Hz, J = 2.7 Hz, 1H, C₅H₂), 4.48 (s, 5H, C₅H₅), 7.60 (s,

1H, OH). ¹³C{¹H} NMR (CDCl₃, δ): 19.2 (CH₃), 19.4 (CH₃), 19.7

(CH₃), 19.8 (CH₃), 21.5 (CH₃), 21.6 (2 C, CH₃), 21.7 (CH₃), 25.81

(CH₂−CH₂), 25.87 (C5/C6), 25.95 (C5/C6), 25.97 (C5/C6), 26.02

(C5/C6), 29.4 (CH₃), 29.7 (CH₃), 29.9 (CH₃), 30.1 (CH₃), 39.24

(C3), 39.26 (C3), 39.4 (d, ³J_C,P= 1.9 Hz, C3), 39.8 (d, ³J_C,P= 1.9 Hz,

C3), 40.4 (C7), 40.9 (C7), 41.0 (C7), 41.1 (C7), 47.83 (C4), 47.85

(C₅H₄), 66.0 (d, J_C,P= 13.8 Hz, C₅H₃), 66.3 (C₅H₄), 67.8 (d, J_C,P

=

2

12.0 Hz, C₅H₃) 87.8 (d, J_C,P= 6.1 Hz, C2), 88.1 (d, J_C,P= 8.7 Hz,

2

C2), 91.3 (d, J_C,P= 7.0 Hz, C2), 118.5 (d, J_C,P= 4.4 Hz, CO_PO),

4

129.5 (d, J_C,P= 10.1 Hz, CO_PO). ³¹P{¹H} NMR (CDCl₃, δ): −4.5

2

3

(PO₄), 22.0 (PO₃, major), 22.2 (PO₃, minor).

O,O,O,O-Tetracyclohexyl 2,2′-Dimethoxy-1,1′-ferrocenediyl Bis-

(phosphonate) (15a). 1,1′-Ferrocenediyl tetracyclohexyl bis-

(phosphate) (13a; 100 mg, 0.14 mmol), diisopropylamine (0.08 mL,

0.57 mmol), BuLi (0.23 mL, 0.58 mmol), TMEDA (0.09 mL, 0.60

mmol), and Me₂SO₄(0.3 mL, 3.2 mmol) were reacted as described in

the general procedure. Puriﬁcation was realized by column

chromatography (silica, 2 × 10 cm) using a 95/5 (v/v) ethyl

3

(C4), 48.09 (C4), 48.12 (C4), 49.1 (d, J_C,P= 6.9 Hz, C1), 49.2 (d,

³J_C,P= 4.9 Hz, C1), 49.4 (d, ³J_C,P= 5.7 Hz, C1), 49.5 (d, ³J_C,P= 4.7 Hz,

C1), 53.8 (dd, ¹J_C,P= 211.0 Hz, ³J_C,P= 11.1 Hz, C−P), 57.5 (dd, ¹J_C,P

= 214.8 Hz, ³J_C,P= 12.3 Hz, C−P), 65.0 (dd, J_C,P= 13.2 Hz, J_C,P= 12.6

2+3

Hz, C₅H₂), 68.9 (pt,

J

= 13.7 Hz, C₅H₂), 72.0 (C₅H₅), 88.6 (d,

C,P

M

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

acetate/methanol mixture as the eluent. Compound 15a was obtained

CH₂), 48.6−49.0 (m, C1), 55.0−55.3 (m, C₅H₃), 56.17−56.21 (m,

1

as an orange oil as a mixture of diastereomers (de = 0.20).

C−P), 56.8 (d, J_C,P= 218.3 Hz, C−P), 57.90−57.94 (OCH₃), 58.1

1

Yield: 70 mg (0.095 mmol, 67% based on 13a). H NMR (CDCl₃,

(C−P), 59.8−60.5 (m, C₅H₄), 62.3−62.5 (m, C₅H₄), 63.7−64.0 (m,

C₅H₃), 66.7−67.8 (m, C₅H₃), 69.2−69.3 (m, C₅H₅), 70.0−70.2 (m,

C₅H₅), 77.6−78.3 (m, C1), 117.6−117.7 (m, C_{C H}−O), 128.3−128.9

δ): 1.18−1.39 (m, 12H, CH₂), 1.43−1.60 (m, 12H, CH₂), 1.63−1.80

(m, 8H, CH₂), 1.87−1.98 (m, 8H, CH₂), 3.71 (s, 3.6H*, OCH₃), 3.83

(s, 2.4H*, OCH₃), 4.12−4.17 (m, 1.6H*, C₅H₃), 4.21−4.22 (m, 1H,

C₅H₃), 4.36−4.43 (m, 4H, Cy_C1, C₅H₃), 4.45−4.57 (m, 3.4H*, Cy_C1,

C₅H₃). ¹³C{¹H} NMR (CDCl₃, δ): 23.5−23.7 (CH₂), 25.1−25.3

(CH₂), 33.5−33.9 (m, CH₂), 57.5 (d, J_C,P= 11.1 Hz, C₅H₃), 58.0

(OCH₃), 58.2 (OCH₃), 58.4 (d, ¹J_C,P=215.6 Hz, C−P), 58.5 (d, ¹J_C,P

=215.1 Hz, C−P), 59.4 (d, J_C,P=11.1 Hz, C₅H₃), 64.8 (d, J_C,P= 13.8

Hz, C₅H₃), 67.8 (d, J_C,P=14.0 Hz, C₅H₃), 68.9 (d, J_C,P=13.1 Hz,

5

4

(m, C_{C H}−O). ³¹P{¹H} NMR (CDCl₃, δ):³²19.8, 20.1, 20.4, 21.0.

5

3

HRMS (ESI-TOF, m/z): calcd for C₃₂H₄₁Fe₂O₄P 632.1437, found

632.1400 [M]⁺.

Crystal data for 10b: C₃₀H₃₇Fe₂O₄P, M_r= 604.26, monoclinic, P2₁,

λ = 0.71073 Å, a = 14.1041(13) Å, b = 5.8359(5) Å, c = 16.704(2) Å, β

= 92.648(9)°, V = 1371.4(2) Å³, Z = 2, ρ_calcd= 1.461 Mg m⁻³, μ =

1.149 mm⁻¹, T = 110.2(6) K, θ range 2.892−24.997°, 5764 reﬂections

collected, 4257 independent reﬂections (R_int= 0.0229), R1 = 0.0908,

wR2 = 0.1454 (I > 2σ(I)), absolute structure parameter²⁸0.02(6).

O-(1S)-Borneyl O-Ferrocenyl (2-Methoxyferrocenyl)phosphonate

(10c). (1S)-Borneyl diferrocenyl phosphate (9c; 100 mg, 0.18 mmol),

diisopropylamine (0.05 mL, 0.36 mmol), BuLi (0.15 mL, 0.38 mmol),

TMEDA (0.05 mL, 0.33 mmol), and Me₂SO₄(0.13 mL, 1.37 mmol)

were reacted as described in the general procedure. Puriﬁcation was

realized by column chromatography (silica, 2 × 10 cm column size)

using an 80/20 (v/v) dichloromethane/ethyl acetate mixture as the

eluent. Compound 10c was obtained as an orange oil as a mixture of

isomers (Table SI2, Supporting Information).

2

C₅H₃), 74.68−74.73 (m, C1), 75.0 (d, J_C,P= 6.2 Hz, C1), 75.22 (d,

²J_C,P= 6.0 Hz, C1), 75.23 (d, ²J_C,P= 6.9 Hz, C1), 129.0 (d, ²J_C,P= 9.8

2

Hz, C_{C H}−O), 129.5 (d, J_C,P= 10.6 Hz, C_{C H}−O). ³¹P{¹H} NMR

5

3

5

3

(CDCl₃, δ): 20.75 (major), 20.81 (minor).

O-Cyclohexyl O-Ferrocenyl (2-Methoxyferrocenyl)phosphonate

(10a). Cyclohexyl diferrocenyl phosphate (9a; 100 mg, 0.18 mmol),

diisopropylamine (0.1 mL, 0.72 mmol), BuLi (0.30 mL, 0.75 mmol),

TMEDA (0.11 mL, 0.73 mmol), and Me₂SO₄(0.3 mL, 3.2 mmol)

were reacted as described in the general procedure. Puriﬁcation was

realized by column chromatography (silica, 2 × 10 cm column size)

using an 85/15 (v/v) dichloromethane/ethyl acetate mixture as the

eluent. Compound 10a was obtained as an orange solid as a mixture of

diastereomers (de = 0.45).

1

Yield: 55 mg (0.089 mmol, 49% based on 9c). H NMR (CDCl₃,

δ): 0.82 (s, 3H, CH₃), 0.83 (s, 3H, CH₃), 0.88 (s, 3H, CH₃), 1.19−

1.33 (m, 3H, CH₂), 1.60−1.64 (m, 1H, H4), 1.66−1.74 (m, 1H, CH₂),

1.91−2.10 (m, 1H, CH₂), 2.12−2.35 (m, 1H, H3), 3.63−3.66 (m, 3H,

OCH₃), 3.71−3.78 (m, 2H, C₅H_3/4), 3.97−4.02 (m, 1H, C₅H_3/4),

4.06−4.12 (m, 5H, C₅H₅), 4.15−4.17 (m, 1H, C₅H_3/4), 4.22−4.40 (m,

8H, C₅H_3/4, C₅H₅), 4.64−4.75 (m, 1H, H2). ¹³C{¹H} NMR (CDCl₃,

Yield: 58 mg (0.10 mmol, 57% based on 9a). Mp: 111−114 °C.

Anal. Calcd for C₂₇H₃₁Fe₂O₄P (562.20): C, 57.68; H, 5.56. Found: C,

57.87; H, 5.66. ¹H NMR (CDCl₃, δ): 1.33−1.43 (m, 3H, CH₂), 1.47−

1.54 (m, 1H, CH₂), 1.58−1.68 (m, 2H, CH₂), 1.72−1.82 (m, 2H,

CH₂), 1.88−2.02 (m, 2H, CH₂), 3.71/3.73 (s, 3H, OCH₃), 3.81−3.85

(m, 2H, C₅H_3/4), 4.04−4.07 (m, 1H, C₅H_3/4), 4.16/4.19 (s, 5H,

C₅H₅), 4.21−4.24 (m, 1H, C₅H_3/4), 4.29−4.31 (m, 1H, C₅H_3/4), 4.32

(s, 5H, C₅H₅), 4.38−4.40 (m, 1H, C₅H_3/4), 4.42−4.47 (m, 1H,

C₅H_3/4), 4.55−4.66 (m, 1H, H1). ¹³C{¹H} NMR (CDCl₃, δ): 23.50

(CH₂), 23.54 (CH₂), 25.24 (CH₂), 25.29 (CH₂), 33.6−33.8 (m,

CH₂), 55.26 (d, J_C,P= 11.6 Hz, C₅H_3/4), 55.31 (d, J_C,P= 11.6 Hz,

δ):³³13.2 (CH₃), 13.3 (CH₃), 18.9 (CH₃), 20.0 (CH₃), 26.5 (C5/

3

C6), 26.6 (C5/C6), 28.10 (C5/C6), 28.12 (C5/C6), 37.2 (d, J_C,P

=

1.3 Hz, C3), 37.6 (d, ³J_C,P= 2.1 Hz, C3), 44.91 (C4), 44.95 (C4), 47.5

3

(C7), 47.6 (C7), 49.7 (d, J_C,P= 6.5 Hz, C1), 49.8 (d, J_C,P= 5.5 Hz,

C1), 55.20 (d, J_C,P= 11.7 Hz, C₅H₃), 55.25 (d, J_C,P= 11.5 Hz, C₅H₃),

56.6 (d, ¹J_C,P= 218.4 Hz, C−P), 56.8 (d, ¹J_C,P= 218.8 Hz, C−P), 58.0

C₅H_3/4), 57.0 (d, ¹J_C,P= 218.0 Hz, C−P), 58.2 (OCH₃), 60.0 (d, J_C,P

=

(OCH₃), 58.1 (OCH₃), 59.9 (d, J_C,P= 3.5 Hz, C₅H₄), 60.0 (d, J_C,P=

3.6 Hz, C₅H_3/4), 60.1 (d, J_C,P= 3.9 Hz, C₅H_3/4), 60.26 (d, J_C,P= 3.3

Hz, C₅H_3/4), 60.33 (d, J_C,P= 3.6 Hz, C₅H_3/4), 62.4−62.5 (m, C₅H_3/4),

63.9 (d, J_C,P= 13.7 Hz, C₅H_3/4), 64.0 (d, J_C,P= 14.6 Hz, C₅H_3/4), 67.2

3.5 Hz, C₅H₄), 60.1 (d, J_C,P= 3.9 Hz, C₅H₄), 60.2 (d, J_C,P= 3.8 Hz,

C₅H₄), 62.36 (C₅H₄), 62.39 (C₅H₄), 62.41 (C₅H₄), 63.99 (d, J_C,P

=

14.7 Hz, C₅H₃), 64.04 (d, J_C,P= 14.6 Hz, C₅H₃), 67.3 (d, J_C,P= 14.2

Hz, C₅H₃), 67.5 (d, J_C,P= 14.6 Hz, C₅H₃), 69.2 (C₅H₅), 69.3 (C₅H₅),

(d, J_C,P= 12.8 Hz, C₅H_3/4), 67.4 (d, J_C,P= 14.1 Hz, C₅H_3/4), 69.27

2

70.07 (C₅H₅), 70.09 (C₅H₅), 82.70 (d, J_C,P= 7.5 Hz, C2), 82.73 (d,

(C₅H₅), 69.33 (C₅H₅), 70.08 (C₅H₅), 70.13 (C₅H₅), 75.7 (d, J_C,P

=

2

²J_C,P= 7.5 Hz, C2), 117.5 (m, C_{C H}−O), 128.5 (d, J_C,P= 9.8 Hz,

6.2 Hz, C1), 76.1 (d, J_C,P= 7.1 Hz, C1), 117.5 (d, J_C,P= 4.8 Hz,

5

4

C_{C H}−O), 128.6 (d, J_C,P= 10.3 Hz, C_{C H}−O). ³¹P{¹H} NMR

2

5

4

5

3

C_C5H3−OCH₃), 128.7 (d, J_C,P= 10.0 Hz, C−OCH₃). ³¹P{¹H} NMR

(CDCl₃, δ): 20.54, 20.61, 21.06, 21.11. HRMS (ESI-TOF, m/z): calcd

for C₃₀H₃₅Fe₂O₄P 602.0967, found 602.0963 [M]⁺.

(CDCl₃, δ): 20.06 (minor), 20.09 (major). HRMS (ESI-TOF, m/z):

calcd for C₂₇H₃₁Fe₂O₄P 562.0654, found 562.0654 [M]+.

Crystal data for 10a: C₂₇H₃₁Fe₂O₄P, M_r= 562.19, monoclinic,

P2₁/c, λ = 0.71073 Å, a = 13.9652(7) Å, b = 8.1909(5) Å, c =

21.2807(12) Å, β = 97.814(5)°, V = 2411.6(2) Å³, Z = 4, ρ_calcd= 1.548

Mg m⁻³, μ = 1.302 mm⁻¹, T = 109.95(10) K, θ range 2.945−24.998°,

O-(1R)-α-Fenchyl O-Ferrocenyl (2-Methoxyferrocenyl)-

phosphonate (10d). (1R)-α-Fenchyl diferrocenyl phosphate (9d;

134 mg, 0.22 mmol), LTMP (130 mg, 0.88 mmol), TMEDA (0.13

mL, 0.86 mmol), and Me₂SO₄(0.3 mL, 3.2 mmol) were reacted as

described in the general procedure. Puriﬁcation was realized by

column chromatography (silica, 2 × 10 cm column size) using a 90/10

(v/v) dichloromethane/ethyl acetate mixture as the eluent. Com-

pound 10d was obtained as an orange oil as a mixture of isomers

(Table SI2, Supporting Information).

11049 reﬂections collected, 4244 independent reﬂections (R_int

0.0399), R1 = 0.0404, wR2 = 0.0913 (I > 2σ(I)).

=

O-Ferrocenyl O-(1R)-Menthyl (2-Methoxyferrocenyl)-

phosphonate (10b). Diferrocenyl (1R)-menthyl phosphate (9b; 200

mg, 0.33 mmol), diisopropylamine (0.09 mL, 0.65 mmol), BuLi (0.27

mL, 0.68 mmol), TMEDA (0.10 mL, 0.66 mmol), and Me₂SO₄(0.2

mL, 2.1 mmol) were reacted as described in the general procedure.

Puriﬁcation was realized by column chromatography (silica, 2 × 10 cm

column size) using a 95/5 (v/v) dichloromethane/ethyl acetate

mixture as the eluent. Compound 10b was obtained as an orange oil as

a mixture of isomers.

1

Yield: 125 mg (0.20 mmol, 91% based on 9d). H NMR (CDCl₃,

δ): 0.93−1.22 (m, 11H, CH₃, CH₂), 1.44−1.55 (m, 2H, CH₂), 1.69−

1.88 (m, 3H, CH₂, CH), 3.38−3.72 (m, 3H, OCH₃), 3.79−3.85 (m,

2H, C₅H₄), 4.04−4.23 (m, 8H, C₅H₅, C₅H₃, H2), 4.25−4.51 (m, 8H,

C₅H₅, C₅H_3/4). ¹³C{¹H} NMR (CDCl₃, δ): 19.18 (CH₃), 19.22

(CH₃), 19.27 (CH₃), 19.31 (CH₃), 21.0 (CH₃), 21.1 (CH₃), 21.2

(CH₃), 21.3 (CH₃), 25.8−26.2 (C5/C6), 29.6−29.8 (CH₃), 39.40 (d,

³J_C,P= 3.0 Hz, C3), 39.45−39.47 (m, C3), 39.6 (d, ³J_C,P= 2.1 Hz, C3),

41.0−41.1 (C7), 47.85 (C4), 47.90 (C4), 47.99 (C4), 48.02 (C4),

1

Yield: 155 mg (0.25 mmol, 74% based on 9b). H NMR (CDCl₃,

δ): 0.74−0.96 (m, 10H, CH₃, CH₂), 1.00−1.09 (m, 1H, CH₂), 1.15−

1.25 (m, 1H, CH₂), 1.32−1.39 (m, 1H, CH), 1.44−1.52 (m, 1H, CH),

1.62−1.71 (m, 2H, CH₂, CH), 2.11−2.49 (m, 2H, CH₂), 3.67−3.72

(m, 3H, OCH₃), 3.78−3.87 (m, 2H, C₅H_3/4), 4.01−4.07 (m, 1H,

C₅H_3/4), 4.11−4.58 (m, 15H). ¹³C{¹H} NMR (CDCl₃, δ): 15.6−15.7

(m, CH₃), 21.1−21.2 (m, CH₃), 22.0−22.1 (m, CH₃), 22.6−22.8 (m,

CH₂), 31.5−31.6 (m, CH₃), 34.07−34.13 (m, CH₂), 43.1−43.4 (m,

3

49.16−49.25 (m, C1), 49.32 (d, J_C,P= 4.7 Hz, C1), 55.0−55.3 (m,

1

C₅H₃), 56.45 (d, J_C,P= 219.7 Hz, C−P), 56.54 (d, J_C,P= 219.1 Hz,

1

C−P), 57.0 (d, J_C,P= 219.6 Hz, C−P), 57.1 (d, J_C,P= 218.3 Hz,

C−P), 57.8−58.0 (OCH₃), 59.8 (d, J_C,P= 3.4 Hz, C₅H₄), 59.8 (d, J_C,P

= 3.4 Hz, C₅H₄), 60.1−60.2 (m, C₅H₄), 60.3−60.4 (m, C₅H₄), 60.6 (d,

N

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

J_C,P= 3.1 Hz, C₅H₄), 62.3−62.4 (m, C₅H₄), 63.8−64.1 (m, C₅H₃),

66.8 (d, J_C,P= 12.3 Hz, C₅H₃), 67.1 (d, J_C,P= 13.2 Hz, C₅H₃), 67.2 (d,

J_C,P= 13.6 Hz, C₅H₃), 67.7 (d, J_C,P= 14.2 Hz, C₅H₃), 69.17−62.22

CH₂), 2.16−2.24 (m, 1H, CH₂), 3.71 (s, 3H, OCH₃), 3.72 (s, 3H,

OCH₃), 3.98−4.00 (m, 1H, C₅H₃), 4.00−4.02 (m, 1H, C₅H₃), 4.13−

4.14 (m, 1H, C₅H₃), 4.18−4.19 (m, 3H, C₅H₃), 4.27 (s, 5H, C₅H₅),

4.31 (s, 5H, C₅H₅), 4.66−4.71 (m, 1H, H2). ¹³C{¹H} NMR (CDCl₃,

δ): 13.04 (CH₃), 18.7 (CH₃), 19.9 (CH₃), 26.4 (C5/C6), 28.2 (C5/

2

(C₅H₅), 69.97−70.00 (C₅H₅), 88.5 (d, J_C,P= 7.3 Hz, C2), 88.95 (d,

2

²J_C,P= 7.4 Hz, C2), 89.02 (d, J_C,P= 7.3 Hz, C2), 89.5 (d, J_C,P= 7.9

3

Hz, C2), 117.7 (d, ²J_C,P= 4.4 Hz, C_{C H}−O), 117.81 (d, ²J_C,P= 4.6 Hz,

C6), 37.5 (C3), 45.1 (C4), 47.3 (C7), 49.8 (d, J_C,P= 6.2 Hz, C1),

5

4

54.6 (d, J_C,P= 8.9 Hz, C₅H₃), 54.7 (d, J_C,P= 8.9 Hz, C₅H₃), 58.0

(OCH₃), 58.1 (OCH₃), 62.2 (d, ¹J_C,P= 158.8 Hz, C−P), 62.7 (d, ¹J_C,P

= 158.4 Hz, C−P), 63.5 (C₅H₃), 63.6 (C₅H₃), 67.0 (d, J_C,P= 14.1 Hz,

C₅H₃), 67.1 (d, J_C,P= 14.5 Hz, C₅H₃), 69.8 (C₅H₅), 69.9 (C₅H₅), 80.4

C_{C H}−O), 117.84 (d, ²J_C,P= 4.4 Hz, C_{C H}−O), 128.41 (d, ²J_C,P= 9.9

5

4

5

4

Hz, C_{C H}−O), 128.44 (d, ²J_C,P= 10.4 Hz, C_{C H}−O), 128.6 (d, ²J_C,P

=

5

3

5

3

10.4 Hz, C_{C H}−O), 129.0 (d, J_C,P= 11.2 Hz, C_{C H}−O). ³¹P{¹H}

2

5

3

5

3

2

(d, J_C,P= 6.4 Hz, C2), 128.8 (d, J_C,P= 7.6 Hz, C_{C H}−O), 129.3 (d,

NMR (CDCl₃, δ): 20.4, 20.7, 20.8, 21.5. HRMS (ESI-TOF, m/z):

5

3

calcd for C₃₁H₃₇Fe₂O₄P 616.1124, found 616.1063 [M]⁺.

²J_C,P= 7.3 Hz, C_{C H}O). ³¹P{¹H} NMR (CDCl₃, δ): 36.8. HRMS (ESI-

5

3

Crystal data for 10d: C₃₁H₃₇Fe₂O₄P, M_r= 616.27, monoclinic, P2₁,

λ = 0.71073 Å, a = 14.7944(13) Å, b = 8.3537(7) Å, c = 22.2802(17)

Å, β = 96.930(7)°, V = 2733.4(4) Å³, Z = 4, ρ_calcd= 1.498 Mg m⁻³, μ =

1.498 mm⁻¹, T = 110.0(3) K, θ range 2.900−24.999°, 22814

reﬂections collected, 9551 independent reﬂections (R_int= 0.1117),

R1 = 0.0679, wR2 = 0.0825 (I > 2σ(I)), absolute structure parameter²⁸

0.01(4).

TOF, m/z): calcd for C₃₀H₃₅Fe₂O₄P 602.0967, found 602.0963 [M]⁺.

O-(1R)-α-Fenchyl Bis(2-methoxyferrocenyl)phosphinate (11d). O-

(1R)-α-Fenchyl O-ferrocenyl (2-methoxyferrocenyl)phosphonate

(10d; 168 mg, 0.27 mmol), diisopropylamine (0.08 mL, 0.55

mmol), BuLi (0.22 mL, 0.55 mmol), TMEDA (0.09 mL, 0.55

mmol), and Me₂SO₄(0.3 mL, 3.16 mmol) were reacted as described

in the general procedure. Puriﬁcation was realized by column

chromatography (silica, 2 × 10 cm column size) using a 98/2 (v/v)

ethyl acetate/methanol mixture as the eluent. Compound 11d was

obtained as an orange oil as a mixture of isomers (Table SI2).

Yield: 171 mg (0.265 mmol, 97% based on 10d). ¹H NMR (CDCl₃,

δ): 0.69−1.12 (m, 11H, CH₃, CH₂), 1.39−1.46 (m, 2H, CH₂), 1.61−

1.67 (m, 1H, H4), 1.71−1.78 (m, 1H, CH₂), 1.85−1.97 (m, 1H, CH₂),

3.55−4.07 (m, 9H, OCH₃, H2, C₅H₃), 4.13−4.43 (m, 14H, C₅H₅,

C₅H₃). ¹³C{¹H} NMR (CDCl₃, δ): 19.1 (CH₃), 19.32 (CH₃), 19.35

rac-O-Cyclohexyl Bis(2-methoxyferrocenyl)phosphinate (rac-

11a) and meso-O-Cyclohexyl Bis(2-methoxyferrocenyl)phosphinate

(meso-11a). The title compounds were obtained as side products

during the synthesis of 10a by reacting cyclohexyl diferrocenyl

phosphate (9a; 100 mg, 0.18 mmol), diisopropylamine (0.1 mL, 0.72

mmol), BuLi (0.30 mL, 0.75 mmol), TMEDA (0.11 mL, 0.73 mmol),

and Me₂SO₄(0.3 mL, 3.2 mmol) as described in the general

procedure. Puriﬁcation was realized by column chromatography (silica,

2 × 10 cm column size) using a 97/3 (v/v) ethyl acetate/methanol

mixture (rac-11a, R_f= 0.42; meso-11a, R_f= 0.38); both compounds

were obtained as orange oils.

(CH₃), 21.2 (CH₃), 21.5 (CH₃), 21.6 (CH₃), 25.8−26.9 (C5/C6),

3

29.3 (CH₃), 29.36 (CH₃), 29.40 (CH₃), 29.7 (CH₃), 39.3 (d, J_C,P

=

1.7 Hz, C3), 39.4 (d, ³J_C,P= 2.1 Hz, C3), 39.6 (d, ³J_C,P= 3.3 Hz, C3),

41.1 (C7), 41.2 (C7), 41.3 (C7), 48.0 (C4), 48.1 (C4), 48.2 (C4),

49.25 (d, ³J_C,P= 3.7 Hz, C3), 49.34 (d, ³J_C,P= 4.8 Hz, C3), 54.3 (d, J_C,P

= 9.9 Hz, C₅H₃), 54.6 (d, J_C,P= 9.3 Hz, C₅H₃), 54.7 (d, J_C,P= 9.0 Hz,

C₅H₃), 54.8 (d, J_C,P= 8.9 Hz, C₅H₃), 57.40 (OCH₃), 57.44 (OCH₃),

57.78 (OCH₃), 57.85 (OCH₃), 58.0 (OCH₃), 58.2 (OCH₃), 61.7 (d,

1

rac-11a: yield 27 mg (0.072 mmol, 39% based on 9a). H NMR

(CDCl₃, δ): 1.32−1.46 (m, 3H, CH₂), 1.49−1.62 (m, 2H, CH₂),

1.69−1.89 (m, 4H, CH₂), 2.05−212 (m, 1H, CH₂), 3.67 (s, 3H,

OCH₃), 3.69 (s, 3H, OCH₃), 3.96−3.97 (m, 2H, C₅H₃), 4.01−4.09

(m, 2H, C₅H₃), 4.14−4.17 (m, 2H, C₅H₃), 4.33 (s, 5H, C₅H₅), 4.34 (s,

5H, C₅H₅), 4.72−4.78 (m, 1H, H1). ¹³C{¹H} NMR (CDCl₃, δ): 23.57

¹J_C,P= 165.7 Hz, C−P), 62.1 (d, ¹J_C,P= 159.1 Hz, C−P), 62.4 (d, ¹J_C,P

= 158.6 Hz, C−P), 62.6 (d, J_C,P= 160.7 Hz, C−P), 63.0 (d, J_C,P

3

(CH₂), 23.61 (CH₂), 25.6 (CH₂), 33.8 (d, J_C,P= 4.1 Hz, CH₂), 34.4

1

(d, ³J_C,P= 3.2 Hz, CH₂), 55.0 (d, J_C,P= 9.4 Hz, C₅H₃), 58.0 (OCH₃),

58.2 (OCH₃), 63.1 (d, J_C,P= 11.6 Hz, C₅H₃), 63.3 (d, ²J_C,P= 12.4 Hz,

=

12.0 Hz, C₅H₃), 63.1 (d, J_C,P= 11.6 Hz, C₅H₃), 63.5 (d, J_C,P= 12.7 Hz,

C₅H₃), 63.7 (d, J_C,P= 12.9 Hz, C₅H₃), 67.1 (d, J_C,P= 15.0 Hz, C₅H₃),

67.3 (d, J_C,P= 15.0 Hz, C₅H₃), 68.8 (d, J_C,P= 9.7 Hz, C₅H₃), 68.8 (d,

J_C,P= 10.2 Hz, C₅H₃), 69.6 (C₅H₅), 69.7 (C₅H₅), 69.8 (C₅H₅), 87.5

(d, ²J_C,P= 7.2 Hz, C2), 87.8 (d, ²J_C,P= 7.2 Hz, C2), 88.0 (d, ²J_C,P= 7.0

1

C₅H₃), 63.6 (d, J_C,P= 161.2 Hz, C−P), 63.8 (d, J_C,P= 155.3 Hz,

C−P), 67.0 (d, J_C,P= 15.1 Hz, C₅H₃), 67.1 (d, J_C,P= 10.7 Hz, C₅H₃),

69.8 (C₅H₅), 69.8 (C₅H₅), 73.7 (d, ²J_C,P= 5.4 Hz, C1), 128.3 (d, ²J_C,P

= 7.8 Hz, C_{C H}−O), 128.6 (d, J_C,P= 10.6 Hz, C_{C H}−O). ³¹P{¹H}

2

5

3

5

3

2

Hz, C2), 129.0 (d, J_C,P= 7.5 Hz, C_{C H}−O), 129.1 (d, ²J_C,P= 7.1 Hz,

NMR (CDCl₃, δ): 34.2.

5

3

1

C

_{C H}O). ³¹P{¹H} NMR (CDCl₃, δ): 35.68, 35.74, 36.7, 38.0. HRMS

meso-11a: yield 40 mg (0.105 mmol, 58% based on 9a). H NMR

(CDCl₃, δ): 1.29−1.33 (m, 3H, CH₂), 1.44−1.47 (m, 1H, CH₂),

1.53−1.60 (m, 1H, CH₂), 1.71−1.78 (m, 2H, CH₂), 1.81−1.89 (m,

2H, CH₂), 3.72 (s, 6H, OCH₃), 4.00−4.02 (m, 2H, C₅H₃), 4.18−4.19

(m, 2H, C₅H₃), 4.22−4.26 (m, 12H, C₅H₅, C₅H₃), 4.46−4.53 (m, 1H,

H1). ¹³C{¹H} NMR (CDCl₃, δ): 23.4 (CH₂), 25.5 (CH₂), 33.8 (d,

³J_C,P= 3.6 Hz, C2/C6), 54.8 (d, J_C,P= 9.0 Hz, C₅H₃), 58.2 (OCH₃),

5 3

(ESI-TOF, m/z): calcd for C₃₂H₃₉Fe₂O₄P 630.1280, found 630.1222

[M]⁺.

General Procedure for the Synthesis of Alkyldichlorophos-

phates 8a−d. The respective alcohols 1a−d (1 equiv) were dissolved

in 10 mL of diethyl ether and cooled to −30 °C. Dropwise addition of

BuLi (1 equiv) resulted in the formation of a colorless precipitate.

After it was stirred for an additional 10 min at −30 °C, the suspension

was added dropwise to a solution containing POCl₃(1 equiv) in 30

mL of diethyl ether at −30 °C. Stirring was continued overnight

followed by ﬁltration through a plug of Celite (min 5 cm) with diethyl

ether to remove the lithium salt. After removal of all volatiles under

reduced pressure, the title compounds 8a−e were obtained as colorless

oils and used without further puriﬁcation.

1

63.1 (d, J_C,P= 158.6 Hz, C−P), 63.6 (d, J_C,P= 12.7 Hz, C₅H₃), 67.0

2

(d, J_C,P= 14.6 Hz, C₅H₃), 69.9 (C₅H₅), 73.8 (d, J_C,P= 6.9 Hz, C1),

2

128.9 (d, J_C,P= 7.8 Hz, C_{C H}−O). ³¹P{¹H} NMR (CDCl₃, δ): 35.6.

5

3

HRMS (ESI-TOF, m/z): calcd for C₂₈H₃₃Fe₂O₄P + Na 599.0708,

found 599.0716 [M + Na]⁺.

O-(1S)-Borneyl Bis(2-methoxyferrocenyl)phosphinate (11c). The

title compound was obtained as a side product during the synthesis of

10c by reacting (1S)-borneyl diferrocenyl phosphate (9c; 100 mg, 0.18

mmol), diisopropylamine (0.05 mL, 0.36 mmol), BuLi (0.15 mL, 0.38

mmol), TMEDA (0.05 mL, 0.33 mmol), and Me₂SO₄(0.13 mL, 1.37

mmol) as described in the general procedure. Puriﬁcation was realized

by column chromatography (silica, 2 × 10 cm column size) using a

95/5 (v/v) ethyl acetate/methanol mixture as the eluent. Compound

11c was obtained as an orange oil as a mixture of diastereomers (Table

SI2, Supporting Information).

Cyclohexyl Dichlorophosphate (8a). Cyclohexanol (1a; 1.8 mL,

17.1 mmol), BuLi (7.4 mL, 18.5 mmol), and POCl₃(4.7 mL, 50

mmol) were reacted as described in the general procedure.

1

Yield: 3.67 g (16.9 mmol, >95% based on 1a). H NMR (CDCl₃,

δ): 1.32−1.45 (m, 3H, CH₂), 1.51−1.56 (m, 1H, CH₂), 1.70−1.84 (m,

4H, CH₂), 1.98−2.06 (m, 2H, CH₂), 4.76−4.83 (m, 1H, H1). ¹³C{¹H}

3

NMR (CDCl₃, δ): 23.2 (CH₂), 24.7 (CH₂), 33.8 (d, J_C,P= 4.9 Hz,

2

C2), 84.1 (d, J_C,P= 9.7 Hz, C1). ³¹P{¹H} NMR (CDCl₃, δ): 5.7.

1

(1R)-Menthyl Dichlorophosphate (8b). (1R)-Menthol (1b; 5.00 g,

32,0 mmol), BuLi (13 mL, 32,5 mmol), and POCl₃(9 mL, 96 mmol)

were reacted by using the general procedure.

Yield: 42 mg (0.067 mmol, 37% based on 9c). H NMR (CDCl₃,

δ): 0.74 (CH₃), 0.80 (CH₃), 0.84 (CH₃), 1.17−1.30 (m, 3H, CH₂),

1.59−1.60 (m, 1H, H4), 1.68−1.76 (m, 1H, CH₂), 2.07−2.14 (m, 1H,

O

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

1

Yield: 8.74 g (32.0 mmol, >95%, based on 1b). H NMR (CDCl₃,

δ): 0.84 (d, ³J_H,H= 6.9 Hz, 3H, CH₃), 0.88−0.96 (m, 7H), 1.01−1.10

(m, 1H), 1.35 (q, ³J_H,H= 11.8 Hz, 1H, H5), 1.43−1.54 (m, 2H), 1.65−

available free of charge via the Internet at http://pubs.acs.org.

Crystallographic data of 4a,b,e, 5e, 6d, 9b, 10a,c,d, and 18 are

also available from the Cambridge Crystallographic Database as

ﬁle numbers CCDC 1024126 (4a), 1024118 (4b), 1024119

(4e), 1024120 (5e), 1024121 (6d), 1024123 (9b), 1024125

(10a), 1024122 (10c), 1024124 (10d), and 1028721 (18).

3

1.76 (m, 2H), 2.08 (dsept, J_H,H= 2.5 Hz, J_H,H=7.0 Hz, 1H, CH),

2.32−2.37 (m, 1H), 4.63 (dtd, ³J_H,P= 10.8 Hz, ³J_H,H= 10.7 Hz, ³J_H,H

=

4.64 Hz, 1H, H1). ¹³C{¹H} NMR (CDCl₃, δ): 15.8 (CH₃), 20.7

3

(CH₃), 21.8 (CH₃), 23.0 (d, J_C,P= 1.7 Hz, CH₂), 25.8 (CH), 31.7

(CH), 33.6 (CH₂), 42.2 (CH₂), 48.2 (d, ³J_C,P= 8.2 Hz, CH₂), 86.7 (d,

²J_C,P= 10.9 Hz, C1). ³¹P{¹H} NMR (CDCl₃, δ): 7.1. HRMS (ESI-

TOF, m/z): calcd for C₁₀H₁₉Cl₂O₂P + Na 295.0392, found 295.0395

[M + Na]⁺.

AUTHOR INFORMATION

■

Corresponding Author

*H.L.: e-mail, heinrich.lang@chemie.tu-chemnitz.de; tel, +49

(0)371-531-21210; fax, +49 (0)371-531-21219.

(1R)-α-Fenchyl Dichlorophosphate (8d). (1R)-α-Fenchol (8d; 4.23

g, 27.4 mmol), BuLi (12 mL, 30 mmol), and POCl₃(8 mL, 85.5

mmol) were reacted as described in the general procedure.

Yield: 7.36 g (27.1 mmol, > 95%, based on 1d). ¹H NMR (CDCl₃,

δ): 0.99 (s, 3H, CH₃), 1.12−1.18 (m, 7H), 1.26−1.28 (m, 1H), 1.48−

1.54 (m, 1H), 1.56−1.59 (m, 1H), 1.69−1.76 (m, 2H), 1.78−1.79 (m,

1H), 4.33 (dd, ³J_H,P= 13.1 Hz, J_H,H= 1.8 Hz, 1H, H2). ¹³C{¹H} NMR

(CDCl₃, δ):19.2 (CH₃), 21.0 (CH₃), 25.65 (C5/C6), 25.73 (C5/C6),

Notes

The authors declare no competing ﬁnancial interest.

ACKNOWLEDGMENTS

■

We are grateful to the Fonds der Chemischen Industrie (FCI)

for generous ﬁnancial support. M.K. and D.S. thank the Fonds

der Chemischen Industrie for a fellowship. We thank

Dipl.Chem. Dieter Schaarschmidt for fruitful discussions.

3

29.6 (CH₃), 39.8 (d, J_C,P= 2.9 Hz, C3), 40.9 (C7), 47.9 (C4), 49.5

(d, J_C,P= 5.9 Hz, C1), 97.0 (d, J_C,P= 11.7 Hz, C2). ³¹P{¹H} NMR

(CDCl₃, δ): 8.4. HRMS (ESI-TOF, m/z): calcd for C₁₀H₁₇Cl₂O₂P +

Na 293.0235, found 293.0252 [M + Na]⁺.

3

2

Synthesis of (R_p)-(2-Methoxyferrocenyl)diphenylphosphane

(17) and (R_p)-(2-Methoxyferrocenyl)diphenylphosphane Oxide

(18). Compound 17 was prepared according to the synthesis protocol

which was reported recently for the racemic mixture.^1aThus, an excess

of Li[AlH₄] (0.6 g, 16 mmol) was treated with trimethylsilyl chloride

(1.65 mL, 12.9 mmol) at −30 °C in tetrahydrofuran (20 mL). After

the suspension was stirred for 5 min, phosphonate 5e (570 mg, 1.00

mmol) was added in a single portion. The mixture was slowly heated

to 50 °C until gas evaporation was no longer detectable. Afterward, the

oil bath was replaced by an ice bath. Acidiﬁcation was realized by

dropwise addition of oxygen-free H₂SO₄(3 mL, ω = 30%). The

mixture was extracted three times with oxygen-free diethyl ether (3 ×

20 mL) under an argon atmosphere. The organic layer was dried over

MgSO₄, and all volatiles were removed under reduced pressure.

Phosphine 17 was dissolved in 6 mL of toluene, and iodobenzene

(0.22 mL, 2.0 mmol), K₃PO₄(425 mg, 2.0 mmol), and [Pd(dppf)Cl₂]

(30 mg, 4 mol %) were added in a single portion. The reaction mixture

was degassed and stirred for 18 h at 110 °C. After the mixture was

cooled to ambient temperature, water (30 mL) was added in a single

portion and the mixture was extracted with diethyl ether (3 × 20 mL).

The organic layer was dried over MgSO₄, and the solvent was removed

under reduced pressure. The residue was puriﬁed by column

chromatography (column size 2 × 10 cm, silica) using a 7/3 (v/v)

hexane/CH₂Cl₂mixture to give 17 (R_f= 0.14) as an orange solid.

HPLC measurements were performed after single recrystallization

from hexane. Yield: 260 mg (0.65 mmol, 65% based on 5e). The

spectroscopic data of phosphane 17 are in agreement with those in the

literature.^1aHPLC (t): rac-17, 26.410 (48.9%), 42.110 (51.1%); (R_p)-

17, 25.485 (>99.9%); ee = 0.99.

REFERENCES

■

(1) (a) Korb, M.; Schaarschmidt, D.; Lang, H. Organometallics 2014,

33, 2099−2108. (b) Schaarschmidt, D.; Lang, H. ACS Catal. 2011, 1,

411−416. (c) Schaarschmidt, D.; Grumbt, M.; Hildebrandt, A.; Lang,

H. Eur. J. Org. Chem. 2014, 6676−6685.

(2) For a recent review, see: (a) Schaarschmidt, D.; Lang, H.

Organometallics 2013, 32, 5668−5704. (b) For an introduction to

ferrocene chemistry, see: Astruc, D. Metallocenes and Sandwich

Complexes in Organometallic Chemistry and Catalysis; Springer-Verlag:

Berlin, 2007; pp 251−288. (c) Schaarschmidt, D.; Lang, H. Eur. J.

Inorg. Chem. 2010, 4811−4821.

(3) (a) Dale, J. A.; Duli, D. L.; Mosher, H. S. J. Org. Chem. 1969, 34,

2543−2549. (b) Parker, D. Chem. Rev. 1991, 91, 1441−1457.

(4) (a) Melvin, L. S. Tetrahedron Lett. 1981, 22, 3375−3376.

(b) Taylor, C. M.; Watson, A. J. Curr. Org. Chem. 2004, 8, 623−626.

(c) Ngono, C. J.; Constantieux, T.; Buono, G. Eur. J. Org. Chem. 2006,

6, 1499−1507. (d) Moulin, D.; Bago, S.; Baudin, C.; Darcel, C.; Juge,

́

S. Tetrahedron: Asymmetry 2000, 11, 3939−3956. (e) Palmacci, E. R.;

Seeberger, P. H. Org. Lett. 2001, 3, 1547−1550. (f) Murai, Y.;

Hashidoko, Y.; Hashimoto, M. Biosci. Biotechnol. Biochem. 2011, 75,

352−354.

(5) (a) Macías, F. A.; Marín, D.; Chinchilla, D.; Molinillo, H. M. G.

Tetrahedron Lett. 2002, 43, 6417−6420. (b) Macías, F. A.; Chinchilla,

D.; Molinillo, H. M. G.; Marín, D.; Varela, R. M.; Torres, A.

Tetrahedron 2003, 59, 1679−1683. (c) Hatano, M.; Miyamoto, T.;

Ishihara, K. J. Org. Chem. 2006, 71, 6474−6484. (d) Clough, J. M.;

Mann, I. S.; Widdowson, D. A. Synlett 1990, 8, 469−470. (e) Zhao, Z.;

Crystals suitable for single-crystal X-ray analysis of phosphanoxide

18 were obtained by recrystallizing 17 from boiling hexane followed by

dissolving 17 (2 mg) in 4 mL of a 95/5 (v/v) hexane/^tBuOMe

mixture. On exposure to atmospheric conditions for 14 days a few

single crystals of 18 could be obtained from this solution.

Crystal data for 18: C₂₃H₂₁FeO₂P, M_r= 416.22, orthorhombic,

P2₁2₁2₁, λ = 0.71073 Å, a = 8.3581(4) Å, b = 8.5846(4) Å, c =

27.2615(14) Å, V = 1956.04(16) Å³, Z = 4, ρ_calcd= 1.413 Mg m⁻³, μ =

0.868 mm⁻¹, T = 110.0(10) K, θ range 2.99−25.50°, 5954 reﬂections

collected, 3481 independent reﬂections (R_int= 0.0336), R1 = 0.0385,

wR2 = 0.0767 (I > 2σ(I)), absolute structure parameter²⁸0.012(19).

Messinger, J.; Schon, U.; Wartchow, R.; Butenschon, H. Chem.

̈

Commun. 2006, 3007−3009. (f) Santos, R. G.; Jesus, A. R.; Caio, J. M.;

Rauter, A. P. Curr. Org. Chem. 2011, 15, 128−148.

(6) (a) Bennett, S. M. W.; Brown, S. M.; Conole, G.; Dennis, M. R.;

Fraser, P. K.; Radojevic, S.; McPartlin, M.; Topping, C. M.;

Woodward, S. J. Chem. Soc., Perkin Trans. 1 1999, 3127−3132.

(b) Chang, C.-W.; Chein, R.-J. J. Org. Chem. 2011, 76, 4154−4157.

(c) Bringmann, G.; Menche, D.; Kraus, J.; Muhlbacher, J.; Peters, K.;

Peters, E.-M.; Brun, R.; Bezabih, M.; Abegaz, B. M. J. Org. Chem. 2002,

̈

67, 5595−5610. (d) Hatano, M.; Ishihara, K. Chem. Rec. 2008, 8, 143−

̀

155. (e) Barta, K.; Francio, G.; Leitner, W.; Lloyd-Jones, G. C.;

Shepperson, I. R. Adv. Synth. Catal. 2008, 350, 2013−2023.

(7) Bonini, B. F.; Femoni, C.; Fochi, M.; Gulea, M.; Masson, S.;

Ricci, A. Tetrahedron: Asymmetry 2005, 16, 3003−3010.

ASSOCIATED CONTENT

■

S

* Supporting Information

(8) Quattropani, A.; Bernardinelli, G.; Kundig, E. P. Helv. Chim. Acta

̈

Text, Tables SI1 and SI2, Figures SI1−5, and CIF ﬁles giving

additional experimental and crystallographic data as well as

spectroscopic details for all new compounds. This material is

1999, 82, 90−104.

(9) Werner, G.; Lehmann, C. W.; Butenschon, H. Adv. Synth. Catal.

2010, 352, 1345−1355.

̈

P

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Organometallics

Article

(10) (a) Hatano, M.; Miyamoto, T.; Ishihara, K. J. Org. Chem. 2006,

71, 6474−6484. (b) Hatano, M.; Ishihara, K. Chem. Rec. 2008, 8, 143−

155.

(11) (a) Price, D.; Simpkins, N. S. Tetrahedron Lett. 1995, 36, 6135−

6136. (b) Nishibayashi, Y.; Arikawa, Y.; Ohe, K.; Uemura, S. J. Org.

Chem. 1996, 61, 1172−1174. (c) Dayaker, G.; Tilly, D.; Chevallier, F.;

Hilmersson, G.; Gros, P. C.; Monging, F. Eur. J. Org. Chem. 2012,

6051−6057.

(30) Schaarschmidt, D.; Lang, H. Organometallics 2010, 29, 4196−

4198.

(31) The chemical shifts of only the main diastereomer are reported.

(32) The chemical shifts of the signals of all four diastereomers are

reported.

(33) Only the signals of the two most intense diastereomers are

reported.

(12) (a) Banks, M. R.; Gosney, I.; Kilgour, D.; Cadogan, J. I. G.;

Hodgson, P. K. G. Heteroat. Chem. 1998, 7, 503−514. (b) Mont-

gomery, H. A. C.; Turnbull, J. H. J. Chem. Soc. 1958, 1963−1967.

(c) Cremlyn, R. J. W.; Ellam, R. M.; Akhtar, N. Phosphorus, Sulfur

Silicon Relat. Elem. 1978, 5, 1−14. (d) Cremlyn, R. J.; Ellam, R. M.;

Akhtar, N. Phosphorus, Sulfur Silicon Relat. Elem. 1979, 7, 109−113.

(e) Garner, C. M.; McWhorter, C.; Goerke, A. R. Tetrahedron Lett.

1997, 38, 7717−7720.

(13) The de was determined by integration and ﬁtting of the signals

of the C₅H₅fragments in the ¹³C(¹H) NMR spectra of 6c, due to

overlapping signals in the ¹H and less intensive signals in the ³¹P{¹H}

NMR spectra.

(14) With addition of Me₂SO₄, 10% of 5e could be isolated with (de

= 0.68).

(15) (a) Heinicke, J.; Kadyrov, R.; Kellner, K.; Nietzschmann, E.;

Tzschach, A. Phosphorus, Sulfur Silicon Relat. Elem. 1989, 44, 209−216.

(b) Heinicke, J.; Bohle, I.; Tzschach, A. J. Organomet. Chem. 1986, 317,

̈

11−21.

(16) The de of the recovered starting material (yield 11%) also

remains at 95%.

(17) For simultaneous rearrangements, see: (a) Huszthy, P.; Farkas,

́ ́ ́

V.; Toth, T.; Szekely, G.; Hollosi, M. Tetrahedron 2008, 64, 10107−

10115. (b) Dhawan, B.; Redmore, D. Synth. Commun. 1987, 17, 465−

468.

(18) (a) Kazul’kin, D. N.; Ryabov, A. N.; Izmer, V. V.; Churakov, A.

V.; Beletskaya, I. P.; Burns, C. J.; Voskoboynikov, A. Z. Organometallics

2005, 24, 3024−3035. (b) Andrieu, J.; Azouri, M. Inorg. Chim. Acta

2007, 360, 131−135. (c) Sasamori, T.; Hori, A.; Kaneko, Y.; Tokitoh,

N. New J. Chem. 2010, 34, 1560−1564. (d) Hiney, R. M.; Higham, L.

J.; Muller-Bunz, H.; Gilheany, D. G. Angew. Chem., Int. Ed. 2006, 45,

̈

7248−7251; Angew. Chem. 2006, 118, 7406−7409. (e) Denis, J. M.;

Forintos, H.; Szelkeb, H.; Keglevich, G. Tetrahedron Lett. 2002, 43,

5569−5571.

(19) (a) Herd, O.; Hessler, A.; Hingst, M.; Tepper, M.; Stelzer, O. J.

Organomet. Chem. 1996, 522, 69−76. (b) Herd, O.; Hessler, A.;

Hingst, M.; Machnitzki, P.; Tepper, M.; Stelzer, O. Catal. Today 1998,

42, 413−420. (c) Machnitzki, P.; Nickel, T.; Stelzer, O.; Landgrafe, C.

Eur. J. Inorg. Chem. 1998, 1029−1034. (d) Brauer, D. J.; Hingst, M.;

Kottsieper, K. W.; Liek, Ch.; Nickel, T.; Tepper, M.; Stelzer, O.;

Sheldrick, W. S. J. Organomet. Chem. 2002, 645, 14−26. (e) Hesser, A.;

Stelzer, O. J. Org. Chem. 1997, 62, 2362−2369. (f) Kumobayashi, H.;

Miura, T.; Sayo, N.; Saito, T.; Zhang, X. Synlett 2001, 1055−1064.

(g) Birdsall, D. J.; Hope, E. G.; Suart, A. M.; Chen, N.; Hu, Y.; Xiao, J.

Tetrahedron Lett. 2001, 42, 8551−8553. (h) Kraatz, H.-B.; Pletsch, A.

Tetrahydron: Asymmetry 2000, 11, 1617−1621.

(20) Burckhardt, J. J. Die Symmetrie der Kristalle; Hauy, R., Ed.;

̈

Birkhauser Verlag: Basel, Switzerland, 1988.

(21) Moss, G. P. Pure. Appl. Chem. 1999, 71, 513−529.

̈

(22) Sheldrick, G. M. Acta Crystallogr., Sect. A 1990, 46, 467−473.

(23) Sheldrick, G. M. Program for Crystal Structure Reﬁnement;

Universitat Gottingen, Gottingen, Germany, 1997.

̈

(24) Sheldrick, G. M. Acta Crystallogr. Sect. A 2008, A24, 112−122.

(25) Farrugia, L. J. J. Appl. Crystallogr. 2012, 45, 849−854.

(26) Santschi, N.; Geissbuhler, P.; Togni, A. J. Fluorine Chem. 2012,

̈

135, 83−86.

(27) The signal was obtained from a concentrated solution of 4b in

C₆D₆. A very concentrated sample of compound 4b in CDCl₃did not

exhibit a signal for the respective carbon atom.

(28) Flack, H. D. Acta Crystallogr., Sect. A 1983, 39, 876.

(29) Nesmayanov, A. N.; Ssasonowa, W. A.; Drosd, V. N. Chem. Ber.

1960, 96, 2717−2729.

Q

dx.doi.org/10.1021/om500953c | Organometallics XXXX, XXX, XXX−XXX

Article Doi

Planar chirality from the chiral pool: Diastereoselective anionic phospho-fries rearrangements at ferrocene

DOI: 10.1021/om500953c

Source and publish data:

Authors:

Article abstract of DOI:10.1021/om500953c

Full text of DOI:10.1021/om500953c

Products guided by the article

R&D Labs maybe for 69145-11-5

Relevant to this article

Hot Product