Synthesis and catalytic applications of new chiral ferrocenyl P,O ligands

Journal of Organometallic Chemistry 691 (2006) 2297–2310

www.elsevier.com/locate/jorganchem

1

*

Nuno Mateus , Lucie Routaboul, Jean-Claude Daran, Eric Manoury

Laboratoire de Chimie de Coordination, CNRS, 205 route de Narbonne, F-31077 Toulouse Cedex, France

Received 3 October 2005; received in revised form 22 November 2005; accepted 22 November 2005

Available online 18 January 2006

Abstract

A new method to synthesize both enantiomers of 2-diphenylphosphino-ferrocenecarboxaldehyde with the phosphine group protected

as a thiophosphine group was developed. These aldehydes react with 1,2 or 1,3 diols to give, in good yields, new chiral phosphine-acetals.

For unsymmetrical (R)-1,3-butanediol, the new asymmetrical acetalic carbon is asymmetric and its conﬁguration was completely con-

trolled by the chirality of the diol. These new P,O ligands were tested in the palladium-catalyzed asymmetric allylic substitution of

1,3-diphenylprop-2-enylacetate. Good yields and enantioselectivities up to 77% were observed. The catalytic performances of two dia-

stereoisomeric ligands with opposite conﬁgurations in planar chirality only proved to be signiﬁcantly diﬀerent, showing a strong inﬂuence

of both planar and central chiralities.

Keywords: Ferrocene; Chiral ligands; P,O ligands; Phosphine; Dioxane; Dioxolane; Asymmetric catalysis; Allylic substitution

1. Introduction

obtained in an enantiomerically pure form. Furthermore,

these ligands belong to the 1,2 disubstituted ferrocene fam-

ily which has produced some of the most successful ligands

used in asymmetric catalysis [9].

The synthesis of these novel ligands, in an enantiomeri-

cally pure form, will be described in this report. The cata-

lytic behavior of these ligands has been examined for the

asymmetric allylic substitution reaction.

In the last three decades, asymmetric catalysis has

attracted much interest because of its huge importance in

synthetic organic chemistry [1]. The design of new chiral

catalysts is essential for exploring new catalytic asymmetric

reactions and for improving existing reactions in terms of

selectivities, especially enantioselectivities but also of activ-

ities, robustness, convenience, etc. Numerous ligands bear-

ing various combinations of heteroelements [1] (P,P; P,N;

N,N; P,S [2] etc. ligands) have been extensively studied.

However, P,O ligands despite their rich coordination chem-

istry [3,4] and a growing importance in catalysis [3,5] are

still rather scarcely used in asymmetric catalysis [6,7]. As

a part of our continuous interest in ferrocene chemistry

[8], we became interested in developing new ferrocenyl

phosphine-acetals P,O ligands. A wide range of such

ligands can be potentially obtained taking into account

the large number of 1,2 or 1,3-diols which can be easily

2. Results and discussion

2.1. Synthesis

In order to obtain our target ligands (10) or (11) (see

Scheme 2), we need an easy access of both enantiomers of

2-diphenylphosphino-ferrocenecarboxaldehyde. Although

the (S) enantiomer can be easily synthesized by a method

developed by Kagan et al. [10], no convenient synthesis is

available, to the best of our knowledge, for the (R)-enantio-

mer. We imagined a synthetic route via the oxidation of a

corresponding alcohol as a protected form to avoid the

phosphine oxidation during the aldehyde synthesis step.

We decided to try to obtain both enantiomers of alcohols

(6) (see Scheme 1) by extending the method successfully

*

Corresponding author. Tel.: +33 5 61 33 31 73; fax: +33 5 61 55 30 03.

E-mail address: manoury@lcc-toulouse.fr (E. Manoury).

Present address: Leverhulme Centre for Innovative Catalysis, Univer-

1

sity of Liverpool, L69 7ZD Liverpool, UK.

doi:10.1016/j.jorganchem.2005.11.053

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N. Mateus et al. / Journal of Organometallic Chemistry 691 (2006) 2297–2310

developed by Weissensteiner et al. for the resolution of 2-

bromodimethylaminomethylferrocene and of 2-iododime-

thylaminomethyl ferrocene with ephedrine as a chiral

auxiliary [11]. Racemic 2-(diphenylthiophosphino) dime-

thylaminomethylferrocene (1) was obtained very eﬃciently

by a published procedure [12]. The reaction of iodomethane

with (1) yielded the ammonium salt (2) quantitatively. The

displacement of trimethylamine by ephedrine was carried

out and the two diasteroisomers (3) and (4) of opposite

planar chirality were obtained in high yields in a 1/1 ratio

(see Scheme 1). Flash chromatography on silicagel allowed

an eﬃcient separation of both diastereoisomers. The planar

chirality of both diastereoisomers (3) and (4) was

determined by X-ray diﬀraction (see below). The transfor-

mation of ferrocenylmethylamines into corresponding

acetoxymethyl ferrocenes by action of acetic anhydride is

a well-established reaction. We also followed this approach

by limiting both reaction times and temperature, and we

found very eﬃcient conditions for the synthesis of the

enantiomerically pure acetate (5) from (3) or (4) (95% yield).

A straightforward saponiﬁcation of (5) yielded both enanti-

omerically pure (R)-(6) or (S)-(6) in high yields. We

unsuccessfully tested several oxidation methods (with man-

ganese dioxide [13], with Dess-Martin reagent [14] and in

Swern conditions [15]) known to allow an eﬃcient oxidation

of primary alcohols into the corresponding aldehydes.

Finally, aldehyde (7) could be eﬃciently synthesized

following a procedure developed by Sharpless et al. using

NMO as oxidant and a ruthenium catalyst [16].

The synthesis of cyclic acetals was successfully carried

out for the 1,2 diols as well as for 1,3 diols (see Table 1)

in toluene in presence of a catalytic amount of the organic

acid, camphorsulfonic acid (CSA) with continuous removal

of water by distillation [17]. In the case of compound (8a),

the new acetalic carbon (carbon 1 of the 1,3-dioxolane ring)

is asymmetric. However, the acetalization reaction yields

one single diastereoisomer. The molecular structure was

determined by X-ray diﬀraction on a single crystal (see Sec-

Scheme 1.

Scheme 2.

N. Mateus et al. / Journal of Organometallic Chemistry 691 (2006) 2297–2310

2299

Table 1

Synthesis of cyclic acetals

middle of C4–C5 bond as showed by the torsion angles

C1–C2–C21–N1 and C3–C2–C21–N1 of À79.5(2)ꢁ and

100.5(2)ꢁ. The S atom is displaced endo towards the Fe

Entry

Diol

Product

Yield^a(%)

˚

atom by 1.293(4) A from the Cp ring. The two Cp rings

1

2

3

4

5

6

a

(R)-1,3-butanediol

(1R,3R)-1,3-pentanediol

(1R,2R)-1,2-butanediol

(8a)

(9a)

(8b)

(9b)

(8c)

(9c)

66

75

63

67

72

76

are nearly eclipsed with a twist angle of 4.9ꢁ and they are

slightly bent with a dihedral angle of 6.04(9)ꢁ.

In both the ephedrine derivatives (3) and (4), the S

atom is displaced endo towards the Fe atom by

Isolated yield.

tion 2.2). The conﬁguration on carbon 1 was determined to

be S (see Fig. 4). As shown in Fig. 2, the dioxolane has a

perfect chair conformation. The conﬁguration on carbon

1 is easily explained by the preferred equatorial position

of the methyl group and essentially of the huge ferrocenyl

group. Similarly, and for the same reasons, the new asym-

metric carbon 1 of the dioxolane ring in (9a) was proved to

have a S conﬁguration (see Fig. 7) as shown by the molec-

ular structure determined by X-ray diﬀraction.

Finally, ligands (10) and (11) were obtained by desulfur-

ization of the corresponding thiophosphines (8) or (9) using

P(NMe₂)₃[8g].

2.2. Crystal structures

Molecular views of the nine compounds (1), (3), (4),

(8a), (8b), (8c), (9a), (9b) and (9c) with atom labelling

schemes are shown in Figs. 1–9. The bond lengths and

angles in all compounds are within expected ranges.

In compound (+/À)-1, the dimethylamino moiety is exo

with respect to the Cp ring and the N atom is nearly

located in the bisecting plane passing through C2 and the

Fig. 1. Molecular view of (+/À)-1 with atom labelling. Ellipsoids

represent 50% probability. H atoms have been omitted for clarity.

Fig. 2. Molecular view of (R_p)-(3) with atom labelling. Ellipsoids represent 50% probability. H atoms not involved in hydrogen bonding have been

omitted for clarity.

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N. Mateus et al. / Journal of Organometallic Chemistry 691 (2006) 2297–2310

Fig. 3. Molecular view of (S_p)-(4) with atom labelling. Ellipsoids represent 50% probability. H atoms not involved in hydrogen bonding have been omitted

for clarity.

Fig. 4. Molecular view of (1S,3R,R_p)-8a with atom labelling. Ellipsoids represent 50% probability. H atoms have been omitted for clarity.

˚

0.766(6) A [1.146(6) A] and 1.261(5) A for (3) and (4),

respectively, whereas the nitrogen atom is exo with

It is worth pointing out that in compound (3), a hydro-

gen bond occurs between the H atom of the hydroxyl

˚

respect to the Cp ring by 1.249(5) and 1.230(4) A for

group and the nitrogen atom [O–H = 0.85(1) A, H–N =

˚

(3) and (4), respectively. The Cp rings are nearly parallel

with a dihedral angle of 0.6(2)ꢁ [2.1(2)ꢁ for molecule 2]

and 3.5(2)ꢁ for (3) and (4), respectively, and they are

nearly eclipsed with a twist angle of 2.4ꢁ [11.9ꢁ] and

5.6ꢁ, respectively.

2.54(4) A, O–N = 2.903(3) A, O–H–N = 107(3)ꢁ] whereas

in compound (4) the hydrogen bond is established with

˚

the sulfur atom [O–H = 0.85(1) A, H–S = 2.639(2) A, O–

S = 3.348(2) A, O–H–S = 147(2)ꢁ] resulting in a diﬀerent

conformation for the ephedrine moiety.

˚

N. Mateus et al. / Journal of Organometallic Chemistry 691 (2006) 2297–2310

2301

Fig. 5. Molecular view of (3R,5R,R_p)-8b with atom labelling. Ellipsoids represent 50% probability. H atoms have been omitted for clarity.

Fig. 6. Molecular view of (3R,4R,R_p)-8c with atom labelling scheme. Ellipsoids represent 50% probability. H atoms have been omitted for clarity.

˚

In the six acetal derivatives (8a), (8b), (8c), (9a), (9b) and

(9c), the chirality of the diols used for the synthesis appears

to be retained in the ﬁnal products.

In compounds (8a), (8b), (9a) and (9b) the dioxane rings

have a chair conformation with the out of plane atoms

being away from the mean plane by À0.627(4) A and

˚

0.661(7) A (8a), À0.668(9) A [À0.60(1) A] and 0.58(1) A

˚

[0.655(9) A] (8b), À0.679(3) A and 0.624(4) (9a) and

˚

À0.560(7) A and 0.653(3) A (9b). In compound (8a) and

(9a), the methyl and the ferrocene moiety are both in

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N. Mateus et al. / Journal of Organometallic Chemistry 691 (2006) 2297–2310

Fig. 7. Molecular view of (1S,3R,S_p)-9a with atom labelling scheme. Ellipsoids represent 50% probability. H atoms have been omitted for clarity.

Fig. 8. Molecular view of (3R,5R,S_p)-9b with atom labelling scheme. Ellipsoids represent 50% probability. H atoms have been omitted for clarity.

equatorial position whereas in (8b) and (9b) the presence of

two methyls results in one being equatorial and the other

axial. These dioxane rings are twisted with respect to the

Cp ring to which they are attached by 68.8(1)ꢁ (8a),

54.3(3)ꢁ [62.3(3)ꢁ] (8b), 42.03(9)ꢁ (9a) and 43.8(2)ꢁ (9b). In

(8a), the methyl substituent on the dioxane ring is oriented

endo towards the Fe atom whereas in (9a) it is oriented exo.

In compounds (8a), (9a) and (9b) the Cp rings are nearly

eclipsed with twist angles of 9.4ꢁ, 3.9ꢁ and 5.1ꢁ, respec-

tively, whereas in compound (8b), the Cp rings have inter-

mediate conformation between eclipsed and staggered with

twist angles of 22.9ꢁ [17.2]. The Cp rings for all compounds

are roughly parallel and the S atoms are always endo

towards the iron atom.

N. Mateus et al. / Journal of Organometallic Chemistry 691 (2006) 2297–2310

2303

Fig. 9. Molecular view of (3R,4R,S_p)-9c with atom labelling scheme. Ellipsoids represent 50% probability. H atoms have been omitted for clarity.

In compounds (8c) and (9c), the dioxolane ring has an

half-chair conformation with the atoms C21–O1–O2–C22

For every ligand studied, good catalytic activities were

observed. The main purpose of this preliminary studies

was to compare the two members of each pair of diastereo-

isomeric ligands (10) and (11) built up from the same chiral

diol or, in other words, to compare the inﬂuence of planar

chirality of the ferrocene moiety, diﬀerent in (10) and (11),

with the inﬂuence of the central chirality from the diol. For

ligands (10a) and (11a), the diﬀerence in enantio-selectivi-

ties observed with the matched ((11a), ee = 53%) and the

mismatched diastereoisomer ((10a), ee = À8%) is high,

indicating that both elements of chirality have a strong

inﬂuence on the stereochemical outcome of the catalytic

reaction. This eﬀect is even more pronounced for ligands

(10c) and (11c) (Table 2, entries 5 and 6). In the case of

ligands (10b) and (11b), the elements of chirality from

(1R,3R)-1,3-pentanediol have a much stronger inﬂuence

than planar chirality on enantio-selectivity (Table 2, entries

being roughly in

a plane (largest deviation being

˚

À0.038(5) and 0.153(4) A, respectively) and the C23 atom

˚

being out of the mean plane by 0.61(1) and 0.44(1) A for

(8c) and (9c), respectively. These planes are twisted with

respect to the Cp ring where they are attached by

81.1(3)ꢁ and 72.0(2)ꢁ for (8c) and (9c), respectively. In

(8c) and (9c) the Cp rings have a conformation between

eclipsed and staggered with twist angles of 20.2ꢁ and

16.2ꢁ, respectively, whereas they are roughly parallel to

each other with dihedral angle of 2.8(4)ꢁ and 3.5(2)ꢁ. The

two methyl groups attached to the dioxolane rings are

trans.

2.3. Catalytic studies

Because some P,O ligands already proved to be good

ligands for the palladium-catalyzed asymmetric allylic sub-

stitution [7], we then decided to explore this reaction as a

preliminary evaluation of the catalytic properties of these

chiral ligands [18]. The reaction of 1,3-diphenylprop-2-enyl-

acetate with the anion of dimethyl malonate in the presence

of [Pd(C₃H₅)Cl]₂(1 mol%) and various chiral ligands (10)

and (11) was tested under classical conditions (see

Scheme 3). The results are summarized in Table 2.

Table 2

Aymmetric allylic substitution with P,O ligands (10) and (11)

Entry

Ligand

Yield^a(%)

ee^b(%)

Conﬁguration

1

2

3

4

5

6

(1S,3R,R_p)-10a

(1S,3R,S_p)-11a

(3R,5R,R_p)-10b

(3R,5R,S_p)-11b

(3R,4R,R_p)-10c

(3R,4R,S_p)-11c

90

94

89

93

95

97

8

53

41

64

18

77

R

S

R

Reactions run with 0.5 mmol of rac-1,3-diphenylprop-2-enyl acetate,

1 mmol of dimethylmalonate, 1 mmol of BSA and a catalytic amount of

base, 0.015 mol of [PdCl(allyl)]₂and 0.03 mol of ligand in 20 mL of

dichloromethane at RT during 16 h.

a

Isolated yield after quantitative conversion.

(R) determined by ¹H NMR using Eu-(+)-(hfc)₃as chiral chemical

b

shift reagent.

Scheme 3.

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N. Mateus et al. / Journal of Organometallic Chemistry 691 (2006) 2297–2310

3 and 4). These preliminary experiments are not suﬃcient

to rationalize the observed enantio-selectivities and com-

plementary investigations are now in progress. In addition,

it is worth pointing out that, with ligand (11c), for instance,

the catalytic system has already achieved a promising level

of enantioselectivity (ee = 77%) before any attempts at

optimization (solvent, temperature, base, ligand/metal

ratio, etc.).

3.1.2. Synthesis of (2-diphenylthiophosphinoferrocenyl)-

trimethylammonium iodide (2)

In an Erlenmeyer ﬂask, 8 g (17.4) of 2-(diphe-

nylthiophosphino)dimethylaminomethylferrocene (1) was

dissolved in 150 ml of ether. 10 ml (161 mmol) of iodom-

ethane was added. The reaction mixture was stirred 1 h

at RT. An abundant yellow solid precipitated. The yellow

solid was ﬁltered in a sintered glass funnel, washed with

ether and dried to yield 9.9 g of yellow solid (95%).

¹H NMR (d (ppm), CDCl₃): 7.80 (2H, m, PPh₂); 7.67

(2H, m, PPh₂); 7.5–7.3 (6H, m, PPh₂); 5.83 (1H, d, AB syst,

J = 13.0 Hz, CH₂); 5.36 (1H, d, AB syst, J = 13.0 Hz,

CH₂); 5.23 (1H, m, subst Cp); 4.61 (1H, m, subst Cp);

4.28 (5H, s, Cp); 4.11 (1H, m, subst Cp); 2.98 (9H, s,

CH₃). ¹³C NMR (d (ppm), CDCl₃): 133.7 (J_PC= 84.4 Hz,

quat PPh₂); 132.09 (J_PC= 87.4 Hz, quat PPh₂); 132.08

(J_PC= 2.8 Hz, PPh₂); 131.93 (J_PC= 10.8 Hz, PPh₂);

131.93 (J_PC= 2.5 Hz, PPh₂); 131.5 (J_PC= 10.2 Hz, PPh₂);

128.9 (J_PC= 12.3 Hz, PPh₂); 128.3 (J_PC= 12.6 Hz, PPh₂);

78.9 (J_PC= 8.5 Hz, quat Cp); 76.9 (J_PC= 12.5 Hz, subst

Cp); 76.5 (J_PC= 11.3 Hz, subst Cp); 73.9 (J_PC= 92.2 Hz,

quat Cp); 72.8 (J_PC= 10.8 Hz, subst Cp); 72.2 (Cp); 63.9

(CH₂); 52.6 (NCH₃). ³¹P NMR (d (ppm), CDCl₃): 40.4.

MS (FAB⁺) m/e: 474 (M cation, 18%),, 415 (M(cation-

NMe₃), 100%).

2.4. Conclusion

We have developed a straightforward synthesis of new

chiral ferrocenyl phosphine-acetals P,O ligands. These

ligands could be obtained with the two possible planar

chiralities (R or S conﬁguration), so the two possible dia-

stereoisomers from the same diol are available for catalytic

evaluations. These new P,O ligands were successfully used

in the palladium-catalyzed asymmetric allylic substitution

of 1,3-diphenylprop-2-enylacetate. A signiﬁcant level of

enantio-selectivity (up to 77%) was achieved. For each pair

of diastereoisomeric ligands with opposite planar chirality,

only the observed enantio-selectivities were signiﬁcantly

diﬀerent, showing a strong mutual inﬂuence of planar

and central chiralities on the catalytic systems.

Further studies in order to develop the coordination

chemistry of these ligands to other metals and to use them

in other catalytic reactions are currently in progress in our

laboratory.

3.1.3. Synthesis of N-(2-diphenylthiophosphinoferrocenyl-

methyl) ephedrine (3) and (4)

In

a

round-bottomed ﬂask, 10 g of (2-diphe-

iodide

3. Experimental

nylthiophosphinoferrocenyl)trimethylammonium

(16.6 mmol) and 10 g of ephedrine (61 mmol) were

dissolved in 350 mL of dry toluene. The solution was

heated to reﬂux with stirring for 3 h. After cooling to

RT, potassium carbonate was added. The reaction mixture

was ﬁltered on paper and the solvents were evaporated.

The crude products were puriﬁed by ﬂash chromatography

on silicagel by using a pentane/ether mixture (1/1, v/v) as

eluent to yield 4.70 g (97%) of each diastereoisomer as a

yellow solid.

3.1. General

All solvents were dried before use. Thin layer chroma-

tography was carried out on Merck Kieselgel 60F254

precoated silicagel plates. Preparative ﬂash chromatogra-

phy was performed on Merck Kieselgel. Instrumentation:

Bruker AM250 and AMX 400 (¹H, ¹³C, and 1P NMR).

3

Elemental analyses were performed by the Service dÕAna-

lyse du Laboratoire de Chimie de Coordination, Toulouse

(France).

First diastereoisomer (R_fc)-(3): ¹H NMR (d (ppm),

CDCl₃): 7.9–7.8 (2H, m, PPh₂); 7.8–7.7 (2H, m, PPh₂);

7.6–7.4 (6H, m, PPh₂); 7.25–7.15 (3H, m, PPh₂); 7.0–6.95

(2H, m, PPh₂); 4.64 (1H, d(AB), J = 12.4 Hz, CH₂); 4.61

(1H, d, J = 3.8 Hz, CH–Ph); 4.52 (1H, m, Cp subst); 4.32

(5H, s, Cp); 4.31 (1H, m, Cp subst); 3.76 (1H, m, Cp subst);

3.37 (1H, br s, OH); 3.27 (1H, d(AB), J = 12.4 Hz, CH₂);

2.84 (1H, qd, J = 6.9 and 3.8 Hz, CH–CH₃); 1.63 (3H, s,

N–CH₃); 0.72 (3H, d, J = 6.9 Hz, CH-CH₃). ¹³C NMR (d

(ppm), CDCl₃): 142.9 (quat Ph); 135.1 (J_P–C= 87.6 Hz,

3.1.1. Synthesis of 2-(diphenylthiophosphino)-

dimethylaminomethylferrocene ((+/À)-1)

The 2-(diphenylthiophosphino)dimethylaminomethyl-

ferrocene was synthesized according to Ref. [12a] and

was sulfurized as described below.

In

a Schlenk tube, under argon, 4 g of crude

2-(diphenylthiophosphino)dimethylaminomethylferrocene

(0.47 mmol) was dissolved in 100 mL of dichloromethane.

1.7 g of sulfur (53 mmol) was then added and the solution

was heated to reﬂux for 2 h. The crude products were

separated by ﬂash chromatography on silicagel with

pentane then ether as eluent to yield 0.89 g of an yellow

solid (Yield = 91% from dimethylaminomethylferro-

cene).The physical data were similar to those published in

Ref. [12b].

quat Ph); 134.1 (J_P–C= 85.6 Hz, quat Ph); 132.5 (J_P–C

10.7 Hz, Ph); 132.4 (J_P–C= 10.5 Hz, Ph) ;131.6 (J_P–C= 3.0

Hz, 2 Ph); 128.6 (J_P–C= 12.5 Hz, Ph); 128.4 (J_P–C

=

12.3 Hz, Ph); 127.9 (Ph); 126.9 (Ph); 126.8 (Ph); 90.3

(J_P–C= 11.7 Hz, Cp quat); 76.2 (J_P–C= 9.8 Hz, Cp subst);

75.6 (J_P–C= 12.4 Hz, Cp subst); 74.5 (CH–Ph); 74.2

(J_P–C= 95.6 Hz, Cp quat); 71.2(Cp); 69.3 (J_P–C= 10.3

Hz, Cp subst); 64.1 (CH–CH₃); 55.5 (CH₂); 37.4 (N–

N. Mateus et al. / Journal of Organometallic Chemistry 691 (2006) 2297–2310

2305

CH₃); 9.3 (CH–CH₃). ³¹P NMR (d (ppm), CDCl₃): 44.1.

[a]_D= À6.5 (CHCl₃, c = 0.5) MS (DCI, NH₃) m/e: 580

(M+1, 100%). Anal. Found: C, 68.25; H, 5.98; N, 2.22%.

C₃₄H₃₆FeNOPS. Calc.: C, 68.38; H, 5.92; N, 2.42.

3.1.5. Synthesis of (R)-(2-diphenylthiophosphinoferrocenyl)

methanol (6)

In an Erlenmeyer ﬂask, a solution of 2.5 g (5.27 mmol)

of R-(5) in 420 mL of methanol was slowly poured into

Second diastereoisomer (S_fc)-(4): ¹H NMR (d (ppm),

CDCl₃): 7.9–7.8 (2H, m, PPh₂); 7.8–7.7 (2H, m, PPh₂);

7.5–7.4 (6H, m, PPh₂); 7.32–7.25 (2H, m, PPh₂); 7.24–

7.18 (3H, m, PPh₂); 4.6–4.5 (3H, m, 1H CH₂1H

CHPh + 1H subst Cp); 4.35 (5H, s, Cp); 4.31 (1H, m, Cp

subst); 3.73 (1H, m, Cp subst); 3.30 (1H, d(AB),

J = 12.9 Hz, CH₂); 3.20 (1H, br s, OH); 2.55 (1H, qd,

J = 6.9 and 3.0 Hz, CH-CH₃); 1.93 (3H, s, N–CH₃); 0.84

(3H, d, J = 6.9 Hz, CH-CH₃). ¹³C NMR (d (ppm), CDCl₃):

143.2 (quat Ph); 134.8 (J_P–C= 87.6 Hz, quat Ph); 134.0

(J_P–C= 85.9 Hz, quat Ph); 132.5 (J_P–C= 10.9 Hz : Ph); 132.4

170 mL of a sodium hydroxide solution in water

(2 mol L^À1). The reaction mixture was vigorously stirred

overnight. After evaporation of methanol, the reaction

mixture was extracted with dichloromethane, washed with

brine and dried on sodium sulfate. The crude product was

then puriﬁed by ﬂash chromatography on silicagel by using

a pentane/ether mixture (1/1, v/v) as eluent to yield 2.17 g

of R-(6) as a yellow solid (yield = 95%). The physical data

were similar to those published in Refs. [8g,19].

3.1.6. Synthesis of (R)-(2-diphenylthiophosphino)-

ferrocenecarboxaldehyde (7)

(J_P–C= 10.8 Hz, Ph); 131.6 (J_P–C= 3.6 Hz,

2

Ph);

128.5 (J_P–C= 12.5 Hz, Ph); 128.4 (J_P–C= 12.3 Hz, Ph);

128.2 (Ph); 126.9 (Ph); 126.4 (Ph); 90.7 (J_P–C= 12.1 Hz,

In a Schlenk tube, 100 mg of N-morpholine oxide

(NMO) was heated at 90 ꢁC under high vacuum for 3 h.

After cooling to RT, 10 mL of dry acetone, 100 mg of alco-

hol R-(6) (0.23 mmol) and 10 mg of [RuCl₂(PPh₃)₃] were

successively introduced under argon. The reaction mixture

was then stirred for 3 h at RT. After evaporation of the

acetone, 20 mL of ether and 20 mL of a 2 N chlorhydric

acid solution were added. The organic phase was washed

with water and dried on sodium sulfate. The crude product

was then puriﬁed by ﬂash chromatography on silicagel by

using a pentane/ether mixture (1/1, v/v) as eluent to yield

85 g of R-(7) (yield = 85%) as a red solid.

Cp quat); 75.9 (J_P–C= 9.8 Hz, Cp subst); 75.7 (J_P–C

=

12.7 Hz, Cp subst); 74.6 (J_P–C= 95.4 Hz, Cp quat); 73.9

(CH-Ph); 71.2(Cp); 69.1 (J_P–C= 10.5 Hz, Cp subst); 65.7

(CH-CH₃); 52.9 (CH₂); 39.4 (N–CH₃); 9.3 (CH-CH₃). ³¹P

NMR (d (ppm), CDCl₃): 44.6. [a]_D= À60.8 (CHCl₃,

c = 0.5) MS (DCI, NH₃) m/e: 580 (M+1, 100%). Anal.

Found: C, 67.93; H, 5.89; N, 2.18%. C₃₄H₃₆FeNOPS.

Calc.: C, 68.38; H, 5.92; N, 2.42.

1

3.1.4. Synthesis of (R)-(2-diphenylthiophosphino-

ferrocenyl)(acetoxy)-methane (5)

(R)-(7): H NMR (d (ppm), CDCl₃): 10.7 (CHO); 7.85–

7.75 (2H, m, PPh₂); 7.7–7.3 (8H, m, PPh₂) ; 5.25 (1H, m,

subst Cp); 4.71 (1H, m, subst Cp); 4.47 (5H, s, Cp); 4.09

(1H, td, J = 2.6 Hz and J = 1.5 Hz, subst Cp). ¹³C NMR

(d (ppm), CDCl₃): 194.1 (CHO); 134.4 (J_PC= 87.8 Hz,

quat PPh₂); 132.7 (J_PC= 86.3 Hz, quat PPh₂); 132.0

(J_PC= 11.0 Hz, PPh₂); 131.8 (J_PC= 10.7 Hz, PPh₂);

131.7 (J_PC= 2.2 Hz, PPh₂); 131.6 (J_PC= 3.0 Hz, PPh₂);

128.5 (J_PC= 12.7 Hz, PPh₂); 128.3 (J_PC= 12.6 Hz,

PPh₂); 82.6 (J_PC= 10.1 Hz, quat Cp); 79.7 (J_PC= 90.7 Hz,

quat Cp); 79.5 (J_PC= 12.9 Hz, subst Cp); 73.2

(J_PC= 10.0 Hz, subst Cp); 71.9 (J_PC= 7.7 Hz, subst Cp);

71.4 (Cp). ³¹P NMR (d (ppm), CDCl₃): 40.6.

[a]_D= +433 (CHCl₃, c = 0.2) MS (EI) m/e: 430 (M,

32%), 337 (53%), 49 (100%). Anal. Found: C, 62.51; H,

3.80%. C₂₃H₁₉FeOPS. Calc.: C, 64.20; H, 4.45.

In a schlenk tube, 2.2 g of N-(2-diphenylthiophosphinof-

errocenylmethyl)ephedrine (3) (3.8 mmol) was dissolved in

100 mL of acetic anhydride (1.06 mmol) under argon. The

solution was stirred for 16 h at 120 ꢁC. After cooling to RT

and removal of the solvent with a high vacuum pump, the

crude products were ﬁltered over silicagel with a pentane/

ether mixture (1/1, v/v) to yield 1.60 g of R-(5) as an orange

solid (Yield = 95%).

¹H NMR (d (ppm), CDCl₃): 7.84–7.77 (2H, m, PPh₂);

7.67–7.61 (2H, m, PPh₂); 7.55–7.43 (4H, m, PPh₂); 7.41–

7.36 (2H, m, PPh₂); 5.57 (1H, d, AB syst, J = 11.8 Hz,

CH₂); 5.03 (1H, d, AB syst, J = 11.8 Hz, CH₂); 4.62

(1H, m, subst Cp); 4.37 (5H, s, Cp); 4.36 (1H, m, subst

Cp); 3.83 (1H, m, subst Cp); 1.55 (3H, s, CH₃). ¹³C

NMR (d (ppm), CDCl₃): 171.0 (CO); 135.3

(J_PC= 87.6 Hz, quat PPh₂); 133.6 (J_PC= 86.0 Hz, quat

PPh₂); 132.4 (J_PC= 10.9 Hz, 2C PPh₂); 131.8 (J_PC

= 2.7 Hz, PPh₂); 131.7 (J_PC= 2.9 Hz, PPh₂); 128.6

(J_PC= 4.1 Hz, PPh₂); 128.5 (J_PC= 3.3 Hz, PPh₂); 85.5

(J_PC= 12.0 Hz, quat Cp); 76.1 (J_PC= 12.3 Hz, subst

Cp); 76.1 (J_PC= 93.6 Hz, quat Cp); 75.6 (J_PC= 8.7 Hz,

subst Cp); 71.2 (Cp); 70.1 (J_PC= 10.3 Hz, subst Cp);

61.7 (CH₂); 20.8 (CH₃). ³¹P NMR (d (ppm), CDCl₃):

44.1. [a]_D= +23.0 (CHCl₃, c = 0.5) MS (DCI, NH₃)

m/e: 475 (M+1, 100%), 415 (M-OAc, 100%). Anal.

Found: C, 63.24; H, 4.89%. C₂₅H₂₃FeOPS. Calc.: C,

63.28; H, 4.89.

3.2. Synthesis of the ligands

3.2.1. General procedure for the preparation of acetals (8)

and (9)

Aldehyde (R_p)-7 (117 mg, 0.27 mmol) was added to a

round-bottomed ﬂask equipped with

a Dean-Stark

apparatus. The system was purged with argon and the

red solid was dissolved in 100 mL of dry toluene. (1R)-

1,3-butanediol (36 mg, 0.4 mmol) and a catalytic amount

of camphorsulphonic acid were then successively added

to the reaction mixture. After heating for 2 h at 110 ꢁC,

the reaction mixture was cooled to room temperature and

2306

N. Mateus et al. / Journal of Organometallic Chemistry 691 (2006) 2297–2310

diluted with 50 mL of dichloromethane. Anhydrous potas-

sium carbonate was added and the mixture stirred for 1 h.

After ﬁltration through celite and evaporation of the sol-

vents, the crude product was then puriﬁed by ﬂash chroma-

tography on silica gel with a pentane/ether mixture (10:1,

v/v) as eluent to yield 91 mg (66%) of acetal as a yellow

solid.

(CH₃). ³¹P NMR (CDCl₃): d 42.1 [a]_D= À32.2 (CHCl₃,

c = 0.2). HR/MS (ES⁺): 539.0870 (calc. M + Na:

539.0873).

(3R,5R,S_p)-9b (Yield = 67%): ¹H NMR (CDCl₃): d 7.84

(2H, m, Ph); 7.68 (2H, m, Ph); 7.55–7.42 (4H, m, Ph), 7.37

(2H, m, Ph); 6.52 (1H, s, OCHO); 4.86 (1H, m, subst Cp);

4.40 (1H, m, subst Cp); 4.37 (5H, s, Cp); 4.33 (1H, m, subst

Cp); 3.85 (1H, m, CH); 3.75 (1H, m, CH); 1.75 (1H, m,

CH₂); 1.49 (3H, d, J = 6.1 Hz, CH₃); 1.25 (1H, m, CH₂);

0.59 (3H, d, J = 6.2 Hz, CH₃). ¹³C NMR (CDCl₃): d

135.0 (J = 88.8 Hz, quat Ph); 133.6 (J = 86.1 Hz quat

Ph); 132.3 (J = 7.1 Hz, Ph); 132.2 (J = 7.2 Hz, Ph); 131.2

(J = 2.9 Hz, Ph); 130.8 (J = 3.0 Hz, Ph); 128.0

(J = 2.3 Hz, Ph); 127.8 (J = 2.8 Hz, Ph); 90.8 (OCHO);

89.8 (J = 11.1 Hz, quat Cp); 75.2 (J = 12.2 Hz, subst Cp);

74.4 (J = 94.6 Hz, quat Cp); 71.0 (Cp); 70.5 (J = 8.8 Hz,

subst Cp); 69.2 (J = 10.4 Hz, subst Cp); 68.8 (CH); 67.7

(CH); 36.7 (CH₂); 21.0 (CH₃); 17.8 (CH₃). ³¹P NMR

(CDCl₃): d 42.8 [a]_D= +25.4 (CHCl₃, c = 0.6). HR/MS

(ES⁺): 539.0884 (calc. M + Na: 539.0873).

(1S,3R,R_p)-8a (Yield = 66%): ¹H NMR (CDCl₃): d 7.84

(2H, m, Ph); 7.63 (2H, m, Ph); 7.55–7.40 (4H, m, Ph), 7.37

(2H, m, Ph); 6.07 (1H, s, OCHO); 4.91 (1H, m, subst Cp);

4.36 (5H, s, Cp); 4.35 (1H, m, subst Cp); 3.91 (1H, m, CH);

3.80 (1H, m, subst Cp); 3.66 (1H, m, OCH₂); 3.61 (1H, m,

OCH₂); 1.59 (1H, m, CH₂CH); 1.37 (1H, m, CH₂CH); 1.30

(3H, d, J = 6.2 Hz, CH₃). ¹³C NMR (CDCl₃): d 135.1

(J = 88.6 Hz, quat Ph); 133.7 (J = 86.4 Hz quat Ph);

132.3 (J = 10.7 Hz, Ph); 132.0 (J = 10.9 Hz, Ph); 131.2

(J = 2.9 Hz, Ph); 130.08 (J = 3.0 Hz, Ph); 128.0

(J = 12.4 Hz, Ph); 127.9 (J = 12.7 Hz, Ph); 97.8 (OCHO);

89.9 (J = 11.2 Hz, quat Cp); 74.9 (J = 12.4 Hz, subst Cp);

74.0 (J = 94.6 Hz, quat Cp); 73.1 (CH); 71.1 (Cp); 70.9

(J = 8.8 Hz, subst Cp); 69.5 (J = 10.3 Hz, subst Cp); 66.5

(OCH₂); 32.9 (CH₂CH); 22.0 (CH₃) ³¹P NMR (CDCl₃): d

42.6 [a]_D= À61.3 (CHCl₃, c = 0.3). HR/MS (ES⁺):

525.0701 (calc. M + Na: 525.0716).

(3R,4R,R_p)-8c (Yield = 72%): ¹H NMR (CDCl₃): d 7.84

(2H, m, Ph); 7.67 (2H, m, Ph); 7.55–7.35 (6H, m, Ph), 6.53

(1H, s, OCHO); 4.80 (1H, m, subst Cp); 4.41 (5H, s, Cp);

4.36 (1H, m, subst Cp); 3.85 (1H, m, subst Cp); 3.59 (1H,

m, CH); 3.45 (1H, m, CH); 1.32 (3H, d, J = 6.0 Hz,

CH₃); 0.95 (3H, d, J = 6.1 Hz, CH₃). ¹³C NMR (CDCl₃):

d 134.9 (J = 78.0 Hz, quat Ph); 133.6 (J = 86.3 Hz quat

Ph); 132.3 (J = 10.8 Hz, Ph); 132.1 (J = 10.9 Hz, Ph);

131.2 (J = 2.9 Hz, Ph); 131.0 (J = 3.0 Hz, Ph); 127.98

(J = 13.4 Hz, Ph); 127.94 (J = 12.7 Hz, Ph); 99.0 (OCHO);

90.1 (J = 11.2 Hz, quat Cp); 79.4 (CH); 77.5 (CH); 75.5

(J = 12.4 Hz, subst Cp); 74.1 (J = 93.8 Hz, quat Cp);

71.1 (J = 8.9 Hz, subst Cp); 71.0 (Cp); 69.4 (J = 10.4 Hz,

subst Cp); 17.1 (CH₃); 16.4 (CH₃). ³¹P NMR (CDCl₃): d

42.2 [a]_D= À94.9 (CHCl₃, c = 0.2). HR/MS (ES⁺):

525.0705 (calc. M + Na: 525.0716).

1

(1S,3R,S_p)-9a (Yield = 75%): H NMR (CDCl₃): d 7.84

(2H, m, Ph); 7.67 (2H, m, Ph); 7.46 (4H, m, Ph), 7.37

(2H, m, Ph); 6.22 (1H, s, OCHO); 4.86 (1H, m, subst Cp);

4.38 (5H, s, Cp); 4.33 (1H, m, subst Cp); 4.19 (1H, dd,

J = 11.3 Hz and 4.8 Hz, OCH₂); 3.94 (1H, m, OCH₂);

3.91 (1H, m, CH); 3.72 (1H, m, subst Cp); 1.58 (1H, m,

CH₂CH); 1.36 (1H, br d, J = 14.9 Hz, CH₂CH); 0.59 (3H,

d, J = 6.2 Hz, CH₃). ¹³C NMR (CDCl₃):

d 135.0

(J = 89.0 Hz, quat Ph); 133.6 (J = 86.2 Hz); 132.25

(J = 10.7 Hz, Ph); 132.18 (J = 10.8 Hz, Ph); 131.2 (J = 2.9

Hz, Ph); 130.8 (J = 3.0 Hz, Ph); 128.0 (J = 12.3 Hz, Ph);

127.8 (J = 12.8 Hz, Ph); 98.2 (OCHO); 89.6 (J = 11.1 Hz,

quat Cp); 75.3 (J = 12.1 Hz, subst Cp); 74.0 (J = 94.6 Hz,

quat Cp); 72.6 (CH); 71.0 (Cp); 70.6 (J = 8.8 Hz, subst

Cp); 69.2 (J = 10.3 Hz, subst Cp); 67.2 (OCH₂); 33.0

(CH₂CH); 20.8 (CH₃) ³¹P NMR (CDCl₃): d 42.7 [a]_D

= +8.6 (CHCl₃, c = 0.5). HR/MS (ES⁺): 525.0699 (calc.

M + Na: 525.0716).

1

(3R,4R,S_p)-9c (Yield = 76%): H NMR (CDCl₃): d 7.84

(2H, m, Ph); 7.66 (2H, m, Ph); 7.55–7.45 (4H, m, Ph), 7.38

(2H, m, Ph); 6.45 (1H, s, OCHO); 4.79 (1H, m, subst Cp);

4.40 (5H, s, Cp); 4.38 (1H, m, subst Cp); 3.87 (1H, m, subst

Cp); 3.67 (1H, m, CH); 3.51 (1H, m, CH); 1.26 (3H, d,

J = 6.1 Hz, CH₃); 1.06 (3H, d, J = 6.0 Hz, CH₃). ¹³C NMR

(CDCl₃): d 135.0 (J = 88.2 Hz, quat Ph); 133.6 (J = 86.4 Hz

quat Ph); 132.4 (J = 10.8 Hz, Ph); 132.2 (J = 11.0 Hz, Ph);

131.3 (J = 2.9 Hz, Ph); 131.0 (J = 3.0 Hz, Ph); 127.94

(J = 12.4 Hz, Ph); 127.92 (J = 12.8 Hz, Ph); 99.1 (OCHO);

89.9 (J = 11.5 Hz, quat Cp); 80.2 (CH); 78.7 (CH); 75.5

(J = 12.4 Hz, subst Cp); 74.9 (J = 94.0 Hz, quat Cp); 71.1

(Cp); 70.5 (J = 8.5 Hz, subst Cp); 69.6 (J = 10.6 Hz, subst

Cp); 17.4 (CH₃); 16.9 (CH₃). ³¹P NMR (CDCl₃): d 42.4

[a]_D= +70.6 (CHCl₃, c = 0.2). HR/MS (ES⁺): 525.0708

(calc. M + Na: 525.0716).

(3R,5R,R_p)-8b (Yield = 63%): ¹H NMR (CDCl₃): d

7.82 (2H, m, Ph); 7.66 (2H, m, Ph); 7.48 (4H, m, Ph),

7.38 (2H, m, Ph); 6.54 (1H, s, OCHO); 4.90 (1H, m, subst

Cp); 4.42 (5H, s, Cp); 4.32 (1H, m, subst Cp); 4.15 (1H, m,

CH); 3.93 (1H, m, CH); 3.61 (1H, m, subst Cp); 1.77 (1H,

m, CH₂); 1.28 (3H, d, J = 6.1 Hz, CH₃); 1.25 (1H, m,

CH₂); 0.98 (3H, d, J = 7.0 Hz, CH₃). ¹³C NMR (CDCl₃):

d 134.6 (J = 88.2 Hz, quat Ph); 133.6 (J = 85.9 Hz quat

Ph); 132.4 (J = 10.8 Hz, Ph); 132.1 (J = 11.8 Hz, Ph);

131.2 (J = 2.9 Hz, Ph); 130.9 (J = 3.0 Hz, Ph); 128.0

(J = 12.4 Hz, Ph); 127.8 (J = 12.7 Hz, Ph); 90.7

(J = 11.8 Hz, quat Cp); 90.5 (OCHO); 74.9 (J = 12.2 Hz,

subst Cp); 74.2 (J = 93.9 Hz, quat Cp); 71.1 (Cp); 70.9

(J = 8.8 Hz, subst Cp); 69.3 (J = 10.2 Hz, subst Cp);

69.0 (CH); 68.0 (CH); 36.8 (CH₂); 22.1 (CH₃); 17.2

3.2.2. General procedure for the desulfurization of the

thiophosphines

In a Schlenk tube, 115 mg of 8a (0.23 mmol) was

dissolved in 5 mL of toluene with 0.2 mL of tris-(dimeth-

N. Mateus et al. / Journal of Organometallic Chemistry 691 (2006) 2297–2310

2307

ylamino)phosphine (5 equiv.). The solution was heated to

reﬂux overnight. After cooling to RT, the solvent was

removed in vacuo. The crude product was then puriﬁed,

under argon, by ﬂash chromatography on silicagel by using

dichloromethane as eluent. 87 mg of pure 10a was obtained

as a yellow solid (93% yield).

(CDCl₃): d 139.7 (J = 8.8 Hz, quat Ph); 137.4 (J = 7.9 Hz

quat Ph); 135.2 (J = 20.9 Hz, Ph); 132.6 (J = 18.2 Hz,

Ph); 129.1 (Ph); 128.1 (J = 7.7 Hz, Ph); 127.6 (J = 6.3 Hz,

Ph); 127.5 (Ph); 92.3 (J = 9.8 Hz, OCHO); 91.0 (J =

20.4 Hz, quat Cp); 75.1 (J = 9.0 Hz, quat Cp); 71.9

(J = 3.4 Hz, subst Cp); 69.9 (Cp); 69.3 (subst Cp); 69.0 (J

= 3.7 Hz, subst Cp); 68.5 (CH); 67.8 (CH); 36.6 (CH₂);

21.2 (CH₃); 17.5 (CH₃). ³¹P NMR (CDCl₃): d À21.0.

(3R,4R,R_p)-10c (Yield = 96%): ¹H NMR (CDCl₃): d

7.57 (2H, m, Ph); 7.40 (3H, m, Ph); 7.23 (5H, m, Ph),

6.12 (1H, d, J = 1.9 Hz, OCHO); 4.64 (1H, m, subst Cp);

4.30 (1H, m, subst Cp); 4.14 (5H, s, Cp); 3.69 (1H, m, subst

Cp); 3.63 (1H, m, CH); 3.49 (1H, m, CH); 1.15 (3H, d,

J = 6.0 Hz, CH₃); 1.11 (3H, d, J = 6.1 Hz, CH₃). ¹³C

NMR (CDCl₃): d 140.2 (J = 10.4 Hz, quat Ph); 137.8

(J = 10.0 Hz quat Ph); 135.2 (J = 21.3 Hz, Ph); 132.5

(J = 18.1 Hz, Ph); 129.1 (Ph); 128.1 (J = 7.7 Hz, Ph);

127.8 (J = 6.0 Hz, Ph); 127.5 (Ph); 101.0 (J = 7.4 Hz,

OCHO); 90.4 (J = 19.8 Hz, quat Cp); 79.8 (CH); 78.0

(CH); 75.1 (J = 12.0 Hz, quat Cp); 72.2 (J = 4.2 Hz, subst

Cp); 70.1 (J = 3.7 Hz, subst Cp); 70.0 (Cp); 69.6 (subst Cp);

16.9 (CH₃); 16.7 (CH₃). ³¹P NMR (CDCl₃): d À21.1.

(3R,4R,S_p)-11c (Yield = 97%): ¹H NMR (CDCl₃): d

7.59 (2H, m, Ph); 7.41 (3H, m, Ph); 7.23 (5H, m, Ph),

6.12 (1H, d, J = 2.2 Hz, OCHO); 4.66 (1H, m, subst Cp);

4.33 (1H, t, J = 2 Hz, subst Cp); 4.12 (5H, s, Cp); 3.73

(1H, m, subst Cp); 3.64 (1H, m, CH); 3.52 (1H, m, CH);

1.26 (3H, d, J = 6.1 Hz, CH₃); 1.14 (3H, d, J = 6.1 Hz,

CH₃). ¹³C NMR (CDCl₃): d 140.4 (J = 9.9 Hz, quat Ph);

137.8 (J = 9.2 Hz quat Ph); 135.4 (J = 21.5 Hz, Ph); 132.4

(J = 17.5 Hz, Ph); 129.2 (Ph); 128.1 (J = 7.8 Hz, Ph);

127.8 (J = 5.8 Hz, Ph); 127.4 (Ph); 100.9 (J = 8.6 Hz,

OCHO); 90.4 (J = 19.7 Hz, quat Cp); 80.6 (CH); 78.4

(CH); 75.3 (J = 11.8 Hz, quat Cp); 72.1 (J = 4.2 Hz, subst

Cp); 70.0 (Cp); 69.9 (subst Cp); 69.4 (J = 3.7 Hz, subst Cp);

17.4 (CH₃); 16.7 (CH₃). ³¹P NMR (CDCl₃): d À21.0.

(1S,3R,R_p)-10a (Yield = 96%): ¹H NMR (CDCl₃): d 7.59

(2H, m, Ph); 7.40 (2H, m, Ph); 7.25–7.15 (6H, m, Ph); 5.56

(1H, s, OCHO); 4.72 (1H, m, subst Cp); 4.30 (1H, m, subst

Cp); 4.09 (5H, s, Cp); 3.91 (2H, m, CH + 1H OCH₂); 3.72

(1H, m, subst Cp); 3.69 (1H, m, CH₂); 1.60 (1H, m, CH₂CH);

1.39 (1H, m, CH₂CH); 1.29 (3H, d, J = 6.2 Hz, CH₃). ¹³C

NMR (CDCl₃): d 140.1 (J = 9.4 Hz, quat Ph); 137.8 (J =

8.5 Hz, quat Ph); 135.2 (J = 21.2 Hz, Ph); 132.4 (J =

17.7 Hz, Ph); 128.1 (J = 7.8 Hz, Ph); 127.7 (J = 6.0 Hz,

Ph); 127.4 (Ph); 99.3 (J = 9.2 Hz, OCHO); 91.3

(J = 21.0 Hz, quat Cp); 74.9 (J = 8.7 Hz, quat Cp); 73.1

(CH); 71.6 (J = 3.5 Hz, subst Cp); 70.6 (Cp); 69.6 (subst

Cp); 69.4 (J = 3.7 Hz, subst Cp); 66.8 (OCH₂); 32.9

(CH₂CH); 21.9 (CH₃) ³¹P NMR (CDCl₃): d À20.7.

(1S,3R,S_p)-11a (Yield = 95%): ¹H NMR (CDCl₃): d

7.58 (2H, m, Ph); 7.40 (3H, m, Ph); 7.25–7.15 (5H, m,

Ph); 5.68 (1H, d, J = 2.4 Hz, OCHO); 4.71 (1H, m, subst

Cp); 4.29 (1H, t, J = 2.5 Hz, subst Cp); 4.27 (1H, m,

OCH₂); 4.10 (5H, s, Cp); 3.93 (1H, td, J = 12.9 Hz,

J = 2.6 Hz, OCH₂); 3.71 (1H, m, subst Cp); 3.67 (1H, m,

CH); 1.63 (1H, m, CH₂CH); 1.43 (1H, m, CH₂CH); 0.78

(3H, d, J = 6.2 Hz, CH₃). ¹³C NMR (CDCl₃): d 139.7

(J = 8.8 Hz, quat Ph); 137.3 (J = 7.8 Hz, quat Ph); 135.2

(J = 26.8 Hz, Ph); 132.6 (J = 18.1 Hz, Ph); 129.1 (Ph);

127.1 (J = 7.8 Hz, Ph); 127.6 (J = 6.2 Hz, Ph); 127.5 (Ph);

99.7 (J = 9.9 Hz, OCHO); 90.9 (J = 21.2 Hz, quat Cp);

74.9 (J = 9.2 Hz, quat Cp); 73.0 (CH); 71.7 (J = 4.0 Hz,

subst Cp); 70.0 (Cp); 69.4 (subst Cp); 69.0 (J = 3.7 Hz,

subst Cp); 67.2 (OCH₂); 32.9 (CH₂CH); 21.1 (CH₃) ³¹P

NMR (CDCl₃): d À21.0.

(3R,5R,R_p)-10b (Yield = 93%): ¹H NMR (CDCl₃): d 7.57

(2H, m, Ph); 7.40 (3H, m, Ph); 7.24 (5H, m, Ph), 5.93 (1H, d,

J = 2.7 Hz, OCHO); 4.76 (1H, m, subst Cp); 4.29 (1H, t,

J = 2.5 Hz, subst Cp); 4.16–4.05 (2H, m, 2CH); 4.12 (5H,

s, Cp); 3.63 (1H, m, subst Cp); 1.77 (1H, m, CH₂); 1.28

(3H, d, J = 6.2 Hz, CH₃); 1.26 (1H, m, CH₂); 1.10 (3H, d,

J = 7.0 Hz, CH₃). ¹³C NMR (CDCl₃): d 139.6 (J = 9.6 Hz,

quat Ph); 137.4 (J = 8.8 Hz quat Ph); 135.2 (J = 20.9

Hz, Ph); 132.7 (J= 18.3 Hz, Ph); 129.1 (Ph); 128.1 (J=7.7 Hz,

Ph); 127.7 (J = 6.2 Hz, Ph); 127.6 (Ph); 91.9 (J = 10.8 Hz,

OCHO); 91.7 (J = 20.6 Hz, quat Cp); 74.9 (J = 8.6 Hz, quat

Cp); 71.3 (J = 4.4 Hz, subst Cp); 70.0 (Cp); 69.5 (subst Cp);

69.2 (J = 3.5 Hz, subst Cp); 68.7 (CH); 68.1 (CH); 36.6

(CH₂); 22.1 (CH₃); 16.8 (CH₃). ³¹P NMR (CDCl₃): d À21.4.

(3R,5R,S_p)-11b (Yield = 93%): ¹H NMR (CDCl₃): d 7.58

(2H, m, Ph); 7.40 (3H, m, Ph); 7.27–7.20 (5H, m, Ph), 5.99

(1H, d, J = 2.4 Hz, OCHO); 4.71 (1H, m, subst Cp); 4.44

(1H, m, CH); 4.28 (1H, t, J = 2.4 Hz, subst Cp); 4.10 (5H,

s, Cp); 3.87 (1H, m, CH); 3.70 (1H, m, subst Cp); 1.80

(1H, m, CH₂); 1.50 (3H, d, J = 7.0 Hz, CH₃); 1.27 (1H,

m, CH₂); 0.73 (3H, d, J = 6.2 Hz, CH₃). ¹³C NMR

3.3. General procedure for palladium-catalyzed allylic

substitution

A mixture of ligand 9 (0.003 mmol), 1,3-diphenylprop-

2-enyl acetate (0.126 g, 0.5 mmol) and [Pd(C₃H₅)Cl]₂

(5.3 mg, 0.0015 mmol) was dissolved in dry dichlorometh-

ane (20 mL). Dimethyl malonate (0.115 mL, 1 mmol),

potassium acetate and BSA (0.250 mL, 1 mmol) were then

added to the resulting solution. The reaction was carried

out at room temperature and monitored by TLC for dis-

appearance of acetate. After complete reaction, the mix-

ture was quenched with a saturated aqueous solution of

ammonium chloride (20 mL). The aqueous phase was

extracted with dichloromethane, the combined organics

were dried over magnesium sulfate, ﬁltered and the sol-

vents evaporated. The conversion was calculated from

the crude reaction mixture by ¹H NMR spectroscopy.

Subsequent puriﬁcation by chromatography on silica elut-

ing with dichloromethane/pentane (1:1) aﬀorded the prod-

uct as colourless oil. The enantiomeric excess was

Table 3

Crystal data and structure reﬁnement

Identiﬁcation code

(+/À)-(1)

3

4

8a

8b

8c

9a

9b

9c

Empirical formula

Formula weight

Temperature (K)

C₂₅H₂₆Fe N P S

459.35

C₆₆H₆₈Fe₂N₂O₂P₂S₂

1158.98

C₃₃H₃₄Fe N O P S

579.49

C₂₇H₂₇Fe O₂P S

502.37

C₂₈H₂₉Fe O₂P S

516.39

C₂₇H₂₇Fe O₂P S

502.37

C₂₇H₂₇Fe O₂P S

502.37

C₂₈H₂₉Fe O₂P S

516.39

C₂₇H₂₇Fe O₂P S

502.37

293(2) K

180(2) K

160(2) K

180(2)

˚

Wavelength (A)

0.71073 A

0.71073

Monoclinic

P2₁

0.71073

Orthorhombic

P2₁2₁2₁

8.8718(17)

15.184(3)

37.500(7)

90

0.71073

Monoclinic

P2₁

0.71073

Orthorhombic

P2₁2₁2₁

9.0578(7)

15.3064(16)

17.2544(14)

90

0.71073

Monoclinic

P2₁

0.71073

Monoclinic

P2₁

Crystal system

Space group

Triclinic

Orthorhombic

P2₁2₁2₁

12.6524(8)

35.827(2)

12.7346(11)

90

Orthorhombic

P2₁2₁2₁

10.5269(7)

12.2372(10)

22.677(2)

90.0

ꢀ

P1

˚

a (A)

8.3085(12)

11.8545(17)

12.6128(18)

103.522(17)

104.951(16)

106.548(17)

1085.3(3)

2

9.0520(8)

11.2472(13)

12.2179(10)

90

9.1705(15)

11.2379(14)

12.426(3)

90

9.2967(9)

12.6384(13)

11.4338(11)

90

8.977(3)

11.215(4)

12.559(3)

90

˚

b (A

˚

c (A)

a (ꢁ)

b (ꢁ)

c (ꢁ)

90

90.0

109.577(9)

90

108.83(2)

90

104.368(8)

90

108.14(3)

90

90.0

90

3

˚

Volume (A )

5772.6(7)

4

2921.2(4)

4

1172.0(2)

2

5051.5(17)

8

1212.1(3)

2

2392.2(4)

4

1301.4(2)

2

1201.6(6)

2

Z

D_calc(Mg/m³)

1.406

1.334

1.318

1.424

1.358

1.376

1.395

1.318

1.388

Absorption

coeﬃcient (mm^À1

0.876

0.677

0.669

0.823

0.766

0.796

0.807

0.743

0.803

)

F(000)

480

2432

1216

524

2160

524

1048

540

524

Crystal size (mm³)

0.77 · 0.75 · 0.63

2.69–28.23

13139

0.8 · 0.64 · 0.34

1.70–20.97

25012

0.64 · 0.64 · 0.16

1.80–24.19

23736

0.8 · 0.44 · 0.08

2.39–26.09

11586

0.356 · 0.139 · 0.035

2.73–26.32

38888

0.25 · 0.25 · 0.003

2.35–26.12

12064

0.37 · 0.33 · 0.043

2.91–32.27

25635

0.39 · 0.266 · 0.077

3.25–32.14

13376

0.54 · 0.46 · 0.033

3.06–26.30

8822

H Range (ꢁ)

Reﬂections collected

Independent

4864 (0.0446)

6119 (0.0348)

4632 (0.0456)

4300 (0.0474)

10302 (0.2063)

4695 (0.1688)

7900 (0.0634)

6769 (0.0488)

4697 (0.0755)

reﬂections (R_int

)

Completeness (%)

Absorption

90.7

99.3

99.1

92.3

99.8

98.3

95.2

93.9

99.8

None

Empirical

Multi-scan

Muli-scan

Multi-scan

correction

Max., min.

0.7672, 0.3465

0.8523, 0.5326

1.0898, 0.5070

0.9295, 0.8568

0.9259 and 0.9035

0.9205, 0.7636

1.00, 0.679

0.9669, 0.7055

transmission

Reﬁnement method

Data/restraints/parameters

Goodness-of-ﬁt

on F²

F²

4864/0/264

1.068

6119/0/697

1.031

4632/0/349

1.001

4300/1/290

1.014

10302/0/299

0.781

4695/1/291

0.832

7900/0/290

0.761

6769/1/300

0.807

4697/1/291

0.831

Final R indices [I > 2r(I)]

R₁= 0.0353,

wR₂= 0.0909

R₁= 0.0423,

wR₂= 0.0987

R₁= 0.0215,

wR₂= 0.0536

R₁= 0.0231,

wR₂= 0.0542

À0.009(9)

R₁= 0.0242,

wR₂= 0.0559

R₁= 0.0282,

wR₂= 0.0570

À0.020(11)

R₁= 0.0347,

wR₂= 0.0868

R₁= 0.0371,

wR₂= 0.0884

À0.025(13)

R₁= 0.0704,

wR₂= 0.0908

R₁= 0.1996,

wR₂= 0.1249

0.00(3)

R₁= 0.0530,

wR₂= 0.0759

R₁= 0.1870,

wR₂= 0.1100

À0.03(4)

R₁= 0.0357,

wR₂= 0.0464

R₁= 0.0800,

wR₂= 0.0518

À0.009(10)

R₁= 0.0383,

wR₂= 0.0650

R₁= 0.0742,

wR₂= 0.0717

0.028(12)

R₁= 0.0523,

wR₂= 0.0982

R₁= 0.0886,

wR₂= 0.1113

0.05(3)

R indices (all data)

Absolute structure parameter

Largest diﬀerence peak

0.352 and À0.436

0.291 and À0.139

0.164 and À0.180

0.631 and À0.709

0.389 and À0.370

0.711 and À1.617

0.255 and À0.286

0.340 and À0.296

0.518 and À0.445

À3

˚

and hole (e A

)

N. Mateus et al. / Journal of Organometallic Chemistry 691 (2006) 2297–2310

2309

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We gratefully acknowledge ﬁnancial support from the

Centre National de la Recherche Scientiﬁque (CNRS).

One of us (N.M.) thanks the European Community (Marie

Curie Training Site Program, Contract Number HPMT-

CT-2001-00398) for a ﬁnancing his stay in Toulouse. We

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Article Doi

Synthesis and catalytic applications of new chiral ferrocenyl P,O ligands

DOI: 10.1016/j.jorganchem.2005.11.053

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