Stereoselective synthesis of phosphoryl-substituted phenols

Article abstract of DOI:10.1002/adsc.201300913

Copper-catalyzed C-X activation-phosphorylation of aryls bearing different groups has been achieved using P(O)-H compounds as efficient phosphorylation reagents without the assistance of any ligand. Optically active H-phosphinates can also act as good substrates in the reaction, giving the (Sp)-phosphoryl substituted phenolic compounds stereospecifically with retention of configuration at the phosphorus center. Furthermore, it is shown that the migration of phosphorus on O-aryl phosphonates from oxygen to carbon also proceeds stereospecifically to produce the corresponding optically active (Rp)-phosphoryl-substituted phenolic compounds with retention of configuration at phosphorus via treatment with lithium diisopropylamide (LDA). Plausible mechanisms have been proposed for these reactions.

Full text of DOI:10.1002/adsc.201300913

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DOI: 10.1002/adsc.201300913
Stereoselective Synthesis of Phosphoryl-Substituted Phenols
Biquan Xiong,a Mei Li,a Yanxi Liu,a Yongbo Zhou,a Changqiu Zhao,b
Midori Goto,c Shuang-Feng Yin,a,* and Li-Biao Hanc,*
a
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan
University, Changsha 410082, Peopleꢀs Republic of China
Fax : (+86)-731-8882-1171; e-mail: sf_yin@hnu.edu.cn
Department of Chemistry, College of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252000,
b
Peopleꢀs Republic of China
National Institute of Advanced Industrial Science and Technology (AIST) Tsukuba, Ibaraki 305-8565, Japan
c
E-mail: libiao-han@aist.go.jp
Received: October 12, 2013; Revised: November 25, 2013; Published online: March 3, 2014
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300913.
À
Abstract: Copper-catalyzed C X activation-phos- cally to produce the corresponding optically active
phorylation of aryls bearing different groups has (Rp)-phosphoryl-substituted phenolic compounds
À
been achieved using P(O) H compounds as efficient with retention of configuration at phosphorus via
phosphorylation reagents without the assistance of treatment with lithium diisopropylamide (LDA).
any ligand. Optically active H-phosphinates can also Plausible mechanisms have been proposed for these
act as good substrates in the reaction, giving the reactions.
(Sp)-phosphoryl substituted phenolic compounds ste-
reospecifically with retention of configuration at the
phosphorus center. Furthermore, it is shown that the Keywords: cross-coupling; migration; optically active
À
migration of phosphorus on O-aryl phosphonates compounds; P(O) H compounds; phosphoryl-substi-
from oxygen to carbon also proceeds stereospecifi- tuted phenols
Introduction
phonate diesters catalyzed by PdACTHUNGETRN(NUG PPh3)4, has been
used for the preparation of various organophosphorus
Organophosphorus compounds are valuable inter- compounds.[8a–c] Although some significant achieve-
mediates in organic synthesis and also find numerous ments in the palladium-catalyzed formation of P C
À
practical applications.[1–6] Some phenolic compounds bonds have been made, the drawbacks of the catalyst
containing phosphoryl functionalities form are usually systems, such as sensitivity to air, high cost, and toxic-
used, e.g., in designing fuel cell membranes,[2] materi- ity, limit their applications.[8d–e] During the past
als with special optical properties.[3,4] Especially those decade, great progress in the copper-catalyzed phos-
compounds bearing chirogenic phosphorus centers phorylation of aryl and vinyl iodides has also been
have wide applications in chiral ligands for asymmet- achieved.[8f–o] Buchwald and Wiemer investigated the
ric catalysis,[5] and bioactive compounds such as herbi- cross-coupling of vinyl bromides with dibutyl phos-
cides,[6a,b] antitumor agents[6c] and modified oligonu- phonate via the assistance of CuI and N,N’-dimethyl-
cleotides.[6d,e] In recent years, there has been a growing ethane-1,2-diamine in 2003.[8k,r] Later, Fu and co-
interest in these kinds of phosphorus compounds.[7] workers reported the synthesis of arylphosphonates,
However, reports related to their preparations are
very limited, and an efficient and stereospecific syn-
thesis of these compounds is highly desired.[8]
As depicted in Scheme 1, transition metal-catalyzed
À
formation of P C bonds by cross-coupling reactions is
a powerful tool for the preparation of numerous im-
portant organophosphorus compounds.[8a–e] Since its
introduction in the early 1980s by Hirao et al., the
cross-coupling reaction of aryl halides with H-phos- tions of aryl halides with nucleophiles.[8]
Scheme 1. Traditional ligand-assisted cross-coupling reac-
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Biquan Xiong et al.
Scheme 2. Outline of our present work.
arylphosphinates, and arylphosphine oxides under cat- sistance of any ligand. By using the optically active
alysis by CuI complexes with l-proline, piperidine-2- (Rp)-H-phosphinates as the precursor, the corre-
À
carboxylic acid, and phenyl hydrogen pyrrolidin-2-yl sponding P C cross-coupling reactions afforded the
phosphonate at 1108C in 2006.[8l–n] However, all these optically active (Sp)-phosphoryl-substituted phenolic
copper-catalyzed cross-coupling reactions strongly compounds stereospecifically with good to excellent
relied on the use of some special ligands (20– yields. Furthermore, we also got the intramolecular
40 mol%), and a ligand-free Cu-catalyzed protocol rearrangement products of (Rp)-phosphoryl-substitut-
À
has not been reported for C P(O) bond formation till ed phenolic compounds through the treatment of op-
now.[8]
tically active O-aryl (Rp)-phosphonates with LDA
Moreover, metalation-induced migration from (Scheme 2). In addition, plausible mechanisms were
oxygen to the aromatic carbon atom in the ortho-lithi- investigated for these reactions.
ated derivatives of phenol is a well-documented pro-
cess for electrophilic groups such as R3Si,[9a]
C(O)R,[9b] or C(O)NR2.[9c] In addition, the migration Results and Discussion
of phosphorus in the ortho-lithiated derivatives of Z-
O-aryl [Z=P(O)(OR)2] and Z-O-diaryl alkyl [Z= Copper-Catalyzed Cross-Coupling of P(O) H
À
P(O)(OR)ACHTUNGTRENNUNG(OAr) phosphates has been investigated in Compounds with Aryl Halides
detail by Melvin in 1981[10a] and Dhawan in 1984.[10h,i]
Further studies on the 1,3-migration of phosphorus We first investigated the reaction of 2-iodophenol
from oxygen to carbon to prepare b-ketophospho- with diisopropyl phosphonate in toluene at 1108C
nates were conducted by Wiemer in 1986.[10g] Later, with the assistance of CuI and l-proline, and the cor-
Welch reported the stereochemistry of the rearrange- responding coupling product of diisopropyl 2-
ment of aryl phosphates to phosphonates in 1,3,2-ox- hydroxy
ACHTUNGTRENNUNG
ACHTUNGTRENUNpNG henylphosphonate 3a was generated in 95%
azaphospholidine 2-oxides.[10l] In addition, Buono and yield (Table 1, entry 1). Then our effort was concen-
Haynes developed the base-induced [1,3]- and [1,2]- trated on optimizing the reaction conditions. In the
intramolecular rearrangements of aryl phosphinates presence of CuI and ligand (e.g., 1,10-phenanthroline,
and phosphinoamidates for preparing the correspond- 8-hydroxyquinoline, 2,2-bipyridine and PPh3), the re-
ing P-chirogenic b-hydroxy tertiary phosphine oxides action gave the desired product in 65–99% yields. In-
and phosphine sulfides in 1998 and 2002, respective- terestingly, when CuI was used alone, we observed
ly.[10m–o] Although a large number of studies for the that the reaction also proceeded efficiently and gave
migration of phosphorus from oxygen to carbon have the corresponding coupling product in 99% yield
been conducted, but the optically active phosphinates (Table 1, entries 2–6). In addition, several copper
have not been reported yet, and the stereochemistry sources such as Cu2O, Cu powder, Cu
and mechanism of the migration of phosphorus from CuCl, and CuO were screened for the reaction. It was
oxygen to carbon is still ambiguous. demonstrated that the use of CuI gave the best cata-
In the present study, we report our findings on the lytic result, and CuX (X=Cl, Br, I) was better than
ACHTUNGRTENUN(NG OAc)2, CuBr,
copper-catalyzed stereospecific cross-coupling of the tested Cu(II) salts [CuO, Cu
P(O) H compounds with aryl halides without the as- tries 6–12).
(OAc)2] (Table 1, en-
À
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Stereoselective Synthesis of Phosphoryl-Substituted Phenols
Table 1. Effects of additives and copper catalysts on the re-
action of P(O) H compounds with aryl halides.
Table 2. Effects of bases, temperature, catalyst loading, and
[a]
À
À
solvents on the reaction of P(O) H compounds with aryl
halides.[a]
Entry
Additive
[Cu]
Yield[b]
Entry
Solvent
Base
Temperature
Yield[b]
1
l-proline
CuI
95%
2
3
4
5
6
7
8
9
1,10-phenanthroline
8-hydroxyquinoline
2,2-bipyridine
PPh3
no additive
no additive
no additive
no additive
no additive
no additive
no additive
CuI
CuI
CuI
CuI
CuI
Cu2O
Cu powder
93%
65%
1
2
3
4
5
6
7
8
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
dioxane
DMF
K2CO3
Na2CO3
K3PO4
Et3N
1108C
1108C
1108C
1108C
1108C
1108C
258C
408C
608C
808C
808C
808C
808C
808C
808C
74%
0%
54%
2%
59%
82%
1%
39%
54%
97%
56%[e]
76%[f]
72%
29%
7%
99%
86% [83%][c]
99%
[c]
Cs2CO3[d]
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
54%
29%
80%
76%
88%
14%
Cu
N
10
11
12
CuCl
CuBr
CuO
9
10
11
12
13
14
15
[a]
Reactions were carried out with 2-iodophenol (1 mmol),
diisopropyl phosphonate (1 mmol), Cs2CO3 (1.5 mmol),
additive (10 mol%), and [Cu] catalyst (10 mol%) in tolu-
ene (2 mL), under an N2 atmosphere with stirring at
1108C for 14 h.
Yield was determined by GC analysis, and dodecane was
used as the internal standard.
20 mol% PPh3 were used.
DMSO
[a]
Reaction conditions: 2-iodophenol (1 mmol), diisopropyl
phosphonate (1 mmol), base (1.5 mmol), CuI (10 mol%),
solvent (2 mL), N2, 14 h, with stirring.
Determined by GC analysis, and dodecane was used as
the internal standard.
Cs2CO3 (0.5 mmol).
Cs2CO3 (1.0 mmol).
CuI (1 mol%).
CuI (5 mol%).
[b]
[c]
[b]
[c]
[d]
[e]
[f]
Various inorganic and organic bases such as K2CO3,
Na2CO3, K3PO4 and Et3N were also tested. Obviously,
Cs2CO3 was the best base for this reaction, and 99%
yield of 3a was obtained at the molar ratio of 2-iodo-
phenol to Cs2CO3 1:1.5 (Table 2, entries 1–6). Addi- 10 mol% CuI as catalyst, 2 mL of toluene as the sol-
tionally, the reaction temperature, catalyst loading vent, 808C, and N2 atmosphere.
and solvents also have a significant influence on the
As shown in Table 3, the cross-coupling can be ap-
À
reaction (Table 2, entries 7–15). When the reaction plied to a variety of aryl halides and P(O) H com-
was carried out at 258C, 1% yield of 3a was generat- pounds. H-Phosphonates bearing ethyl, isopropyl or
ed. Within the range 25–808C, an increment of tem- n-butyl groups could couple efficiently with 2-iodo-
perature was beneficial for this reaction, while the in- phenol to afford the coupling products in good to ex-
crease of temperature from 808C to 1108C did not cellent yields. tert-ButylACHTNUGTRNEUNG(phenyl)phosphine oxide and
result in an increase in yield of the expected product. diphenylphosphine oxide also exhibited high reactivi-
Therefore, the optimal temperature was selected at ty, producing the corresponding products in 94% and
808C (Table 1, entry 6, Table 2, entries 7–10). On the 96% yields, respectively. In addition, some halogen-
other hand, when only 1 mol% of CuI and Cs2CO3 substituted phenols were examined, including 2-bro-
(1.5 equiv.) were used, the reaction of 1a with 2a gave mophenol, 1-bromonaphthalen-2-ol, 2-bromo-4-fluo-
3a in 56% yield. With the increase of CuI from rophenol, 2,6-dibromo-4-[2-(3,5-dibromo-4-hydroxy-
1 mol% to 5 mol%, 76% yield of 3a was gained. Thus phenyl)propan-2-yl]phenol, 2-bromo-4-methoxyphe-
the best loading of CuI should be 10 mol% (Table 2, nol and 2,4,6-tribromophenol. The reaction of 1-bro-
entries 11 and 12). Moreover, different solvents in- monaphthalen-2-ol with 2a produced the desired
cluding toluene, dioxane, DMF and DMSO were ex- product only in 27% yield, which may be ascribed to
amined for this reaction. It is clear that the best sol- the low solubility and lower reactivity of halogen-sub-
vent for this reaction was toluene (Table 2, entries 13– stituted naphthols. But the use of 2-bromo-4-fluoro-
15). Therefore, the optimal reaction conditions are as phenol and 2-bromo-4-methoxyphenol showed good
À
follows: 1 mmol of aryl halides, 1 mmol of P(O) H coupling yields. Comparatively, a 94% yield of 3h was
compounds, 1.5 equivalents of Cs2CO3 as base, obtained from the reaction of 2-bromo-4-fluorophenol
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[a]
À
Table 3. Copper-catalyzed cross-coupling of P(O) H compounds with aryl halides.
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Stereoselective Synthesis of Phosphoryl-Substituted Phenols
Table 3. (Continued)
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Table 3. (Continued)
[a]
À
Reaction conditions: halogen-substituted phenol (1 mmol), P(O) H compound (1 mmol),
Cs2CO3 (1.5 mmol), CuI (0.1 mmol), toluene (2 mL), N2, 808C, 14–20 h.
Isolated yields.
[b]
[c]
[d]
[e]
[f]
Yield was determined by GC analysis, dodecane was used as the internal standard.
1108C.
2 mmol of 2a were used, 1108C.
5 mol% CuI were used.
ND=not detected.
[g]
with diphenylphosphine oxide due to the higher reac- configuration at the phosphorus center in Rp-2f
tivity of secondary phosphine oxides than H-phospho- (Figure 1).
nates. For most cases, electron-donating groups
Simultaneously, different aryl halides, such as 2-io-
(Table 3, entry 11) or electron-withdrawing groups doaniline (1h), 2-bromobenzenethiol (1i), 2-chloro-
(Table 3, entries 8, 10, 12) on the aryl halides did not
À
change the yields of the P C cross-coupling products
significantly. Furthermore, 3i was generated in 76%
yield from the reaction of 1e with 2a, while the use of
2,4,6-tribromophenol only produced the monocou-
pling product of 3k. This phenomenon may be ex-
plained by the fact that the aromatic ring of 3k bear-
ing an electron-withdrawing group has a lower redox
potential than the aromatic ring of 1e, leading to no
product from the dual cross-coupling reaction of 1g
with 2a.
It is worth noting that the current cross-coupling re-
actions all proceed highly stereospecifically with the
retention of configuration at the phosphorus center,
thus can be applied in the preparation of enantiomeri-
cally pure (Sp)-phosphoryl-substituted phenolic com-
pounds by employing the easily accessible optically
pure H-phosphinate such as (À)-menthyl phenylphos-
phinate Rp-2f (Rp/Sp> 99:1) and (À)-menthyl benzyl-
phosphinate Rp-2g (Rp/Sp> 99:1) as the starting ma-
terials. Both 2-iodophenol (1a) and 2-bromophenol
(1b) can be used to react with the optically active H-
phosphinate Rp-2f and Rp-2g, giving the desired prod-
ucts in 57–89% yields stereospecifically. Additionally,
Figure 1. ORTEP drawing of compound (Sp)-3n. Hydrogen
the reaction of 1-bromonaphthalen-2-ol (1c) with Rp-
atoms are omitted for clarity; ellipsoids are drawn at 50%
(À)-menthyl phenylphosphinate Rp-2f can afford the
coupling product Sp-3n (Rp/Sp> 99:1) in a yield of up
to 53% (Table 1, entries 13–16). In addition, the ste-
reochemistry at phosphorus was confirmed by X-ray
analysis of compound Sp-3n, which unambiguously
À
probability. Selected bond lengths [ꢂ] and angles [deg]: P1
O1 1.484(2), O2 P1 1.570(3), P1 C11 1.777(4), P1 C1
À
À
À
À
À
À À
1.793(4), C17 O2 1.480(5), C2 O3 1.351(4); O1 P1 C1
108.53(16), O1 P1 O2 110.50(18), O1 P1 C11 110.50(18),
C17 O2 P1 125.1(2), O2 P1 C11 101.70(14), C2 C1 P1
À
À
À À
À
À
À
À
À
À
À
À
À À
shows that the reaction proceeds with retention of 119.5(3), C10 C1 P1 122.7(2), C11 P1 C1 111.08(17).
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Stereoselective Synthesis of Phosphoryl-Substituted Phenols
Scheme 3. A plausible mechanism for the copper-catalyzed cross-coupling reaction.
phenol (1j), 2-bromo-4-nitrophenol (1k), iodobenzene (Sp)-phosphoryl-substituted phenolic compounds. In-
(1l) and bromobenzene (1m), were investigated for terestingly, through the metalation-induced rearrange-
this reaction. 2-Iodoaniline (1h) and iodobenzene (1l) ment of optically active (Rp)-O-aryl phosphonates,
were good substrates in the reaction, affording the we also obtained the corresponding rearranged prod-
corresponding products in 91–94% yields, respective- ucts of (Rp)-phosphoryl-substituted phenolic com-
ly. However, the use of 2-bromobenzenethiol (1i), 2- pounds. It is worth noting that both of the reactions
chlorophenol (1j), 2-bromo-4-nitrophenol (1k), bro- described above employed the (Rp)-H-phosphinates
mobenzene (1m) and o-bromoanisoles (1n) did not as the starting materials.
generate the expected products. It is deduced that
ArCls are too unreactive toward oxidative addition,
and when the phenolate is absent or too stable, the Stereospecific Migration of Phosphorus from Oxygen
reaction does not work. Compared with the previous to Carbon
report, the present catalytic system shows the advant-
À
age that some aryl halides can react with P(O) H The metalation-induced migration of phosphorus
compounds efficiently without the use of some special from oxygen to carbon atom can be applied to a varie-
ligands.[8f–o]
ty of functionalized optically active phosphonates. Ac-
A possible mechanism for the cross-coupling reac- cording to our previous report,[11d] we allowed some
À
tion of aryl halides with P(O) H compounds is pro- P-chirogenic phosphonates to react with LDA, and
posed in Scheme 3. The halogen-substituted phenol A the corresponding (Rp)-phosphoryl-substituted phe-
combines with Cu+ firstly to form the copper-pheno- nolic compounds were obtained with good to excel-
late intermediate C via the oxidative addition in the lent yields (Table 4, entries 1–14). Aryl-substituted
presence of Cs2CO3. Simultaneously, the copper-phe- optically active phosphonates bearing different groups
nolate intermediate C undergoes the tautomerization such as alkyl, alkoxy, nitro- and trifluoromethyl
to generate the unstable CuACTHNUTRGNE(NUG III) intermediate D. groups all can efficiently undergo the rearrangement
Then the P(O)À ion couples with D to generate the to afford the corresponding products in high yields
intermediate E efficiently in the presence of base. (Table 4, entries 1–10). The rearrangement of (À)-
À
The final P C bond formation via the reductive elimi- menthyl O-naphthalen-5-yl phenyl phosphonate (Rp-
nation completes the catalytic cycle by regenerating 4k, Rp/Sp>99:1) also proceeds smoothly to yield the
Cu+ as a catalytically active species and with retention product of (À)-menthyl phenyl(1-hydroxynaphthalen-
of configuration at the phosphorus center.
2-yl)-2-phosphinate (Rp-5k, Rp/Sp> 99:1) in 91% iso-
As discussed above, by employing the cross-cou- lated yield (entry 11). Moreover, the mixture of Rp-5l
pling reaction of optically active H-phosphinates with (Rp/Sp> 99:1)/Rp-5l’ (Rp/Sp> 99:1) in ratio of 82/18
aryl halides, we successfully synthesized a series of was also obtained in 93% yield from the rearrange-
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Table 4. Stereospecific migration of phosphorus from oxygen to carbon to prepare the Rp-phosphoryl-sub-
stituted phenolic compounds.[a]
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Table 4. (Continued)
[a]
Optically active (Rp)-phosphonate (0.5 mmol) was slowly added to a newly prepared lithium
diisopropyl
G
stirred for 1 h and then slowly warmed to room temperature.
[b]
[c]
Isolated yield.
ND=not detected.
ment of (À)-menthyl O-naphthalen-6-yl phenyl phos- (À)-menthyl diphenyl 1,4-phenylene diphosphonate
phonate (Rp-4l, Rp/Sp> 99:1) (entry 12). Additional- (Rp-4n, Rp/Sp> 99:1) with LDA (entry 14). Howev-
ly, di-(À)-menthyl phenyl (phenyl) (2,5-dihydroxy- er, the use of (À)-menthyl O-phenyl benzylphospho-
phenyl)-bis-phosphinate (Rp-5n, Rp/Sp> 99:1) bear- nate (Rp-4q, Rp/Sp> 99:1) did not give the expected
ing two P-chirogenic centers was successfully synthe- product under the present reaction conditions, un-
sized in 92% isolated yield from the treatment of di- doubtedly due to the higher activity of the sp3-H of
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CH2 in the benzyl group than the ortho-sp2-H in the
À
aryl ring. It was obvious that, when the P O aryl ring
was substituted with a functional group at the ortho/
para-situation or without any substituted groups on
the aryl ring, the migration product was produced
without any selectivity on the ortho-situation (en-
À
tries 1–7). But for the P O aryl ring substituted with
a functional group at the meta-situation on the aryl
ring, the migration is prone to generate the 2-hy-
droxy-4-functional substituted group aryl phosphi-
nates, which may be due to the ortho-substituted
steric hindrance (entries 8–10).
On the other hand, (À)-menthyl 2,4,6-trimethylphe-
nyl O-phenyl phosphonate (Rp-4o, Rp/Sp=97:3) and
(À)-menthyl 2,4,6-trimethylphenyl O-4-methoxyphen-
yl phosphonate (Rp-4p, Rp/Sp=97:3) cannot proceed
the rearrangement under the present reaction condi-
tions. But when (À)-menthyl 2,4,6-trimethylphenyl O-
4-trifluoromethylphenyl phosphonate (Rp-4m, Rp/
Sp=97:3) was applied in this reaction, the expected
rearranged product was obtained in 82% isolated
yield (Table 4, entries 13, 15, 16). It was deduced that
this phenomenon may be ascribed to the electronic
effect on the aryl ring. If the aryl ring was substituted
with an electron-donating group or without any sub-
stituted functional groups, the reactivity of the ortho-
proton linked in the aryl ring (sp2-H) may be lower
than that of the proton in the mesityl methyl group
(sp3-H). Therefore, it was speculated that the base
(LDA) could not lithiate the ortho-proton in the aryl
ring to form the metalation-induced unstable inter-
Figure 2. ORTEP drawing of compound (Rp)-5c. Hydrogen
atoms are omitted for clarity, ellipsoids are drawn at 50%
À
probability. Selected bond lengths [ꢂ] and angles [deg]: P1
À
À
À
O1 1.580(9), P1 O2 1.491(10), P1 C11 1.799(13), P1 C21
À
À
À
À À
1.790(14), C1 O1 1.463(15), O1 P1 O2 114.58(5), O1 P1
À
À
À À
C11 107.63(6), O1 P1 C21 103.68(6), O2 P1 C11
À
À
À À
110.10(6), O2 P1 C21 110.14(6), C11 P1 C21 110.51(6),
À
À
C1 O1 P1 122.43(8).
mediate to accelerate the rearrangement. If the aryl Rp-4r (Rp/Sp>99:1) could undergo the metalation-
ring was substituted with a strong electron-withdraw- induced rearrangement to yield the product of 2-hy-
ing group (e.g., trifluoromethyl), the reactivity of the droxyphenyl (À)-menthyl 2-phenylpropan-2-yl phos-
proton linked in the aryl ring (sp2-H) may be higher phinate (Rp-5r, Rp/Sp>99:1) in 91% isolated yield
than the one linked in the mesityl methyl group (sp3- (Scheme 4).
H), and the metalation-induced rearrangement could
We further operated the reaction of diastereomeric
proceed smoothly to generate the product. The ste- (À)-menthyl phenyl H-phosphinate (Rp/Sp=52/48)
reochemistry at phosphorus of compound Rp-5c (Rp/ with phenol under the Atherton–Todd reaction condi-
Sp>99:1) was confirmed by X-ray analysis, unambig- tions, and the enantiomer product (À)-menthyl O-
uously demonstrating that this type of metalation-in-
duced rearrangement reaction proceeds with reten-
tion of configuration at the phosphorus center in Rp-
4c (Rp/Sp>99:1) (Figure 2).
As discussed above, the optically active phospho-
nate Rp-4q (Rp/Sp>99:1) could not undergo the met-
alation-induced rearrangement under the present re-
action conditions (Table 1, entry 17), plausibly due to
the reactivity of the sp3-H of CH2 in benzyl being
higher than that of the ortho-sp2-H in aryl ring. Thus,
we further operated the di-methylation reaction of
(À)-menthyl O-phenyl benzyl phosphonate (Rp-4q,
Rp/Sp>99:1) through the treatment of LDA and
MeI, and the expected product (À)-menthyl O-phenyl
2-phenylpropan-2-yl phosphonate (Rp-4r, Rp/Sp>
Scheme 4. Dimethylation of P-chirogenic phosphonate
(Rp)-4q and the subsequent metalation-induced rearrange-
99:1) was obtained in 92% isolated yield. Moreover,
the corresponding optically active phosphonate of ment.
790
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Stereoselective Synthesis of Phosphoryl-Substituted Phenols
phenyl phenyl phosphonate (4s, Rp/Sp=52/48) was
gained in 92% isolated yield.[11d] In addition, 2-hy-
droxyphenyl (À)-menthyl phenyl phosphinate (5s, Rp/
Sp=52/48) was also obtained in 95% isolated yield
from the reaction of (À)-menthyl phenyl phenyl phos-
phonate (4s, Rp/Sp=52/48) with LDA (Scheme 5).
Thus it was deduced that this reaction proceeded ste-
reospecifically.
Finally, as depicted in Scheme 6, in order to clarify
the reaction mechanism, we used two different types
of phosphates as starting materials, such as diethyl 4-
methoxyphenyl phosphate (4t) and diisopropyl phenyl
phosphate (4u), which were treated with LDA under
the same reaction conditions. After the reaction was
complete, only two types of desired products – diethyl
2-hydroxy-5-methoxyphenylphosphonate (5t) and di-
ACHTUNGTRENNUNGisopropyl 2-hydroxyphenylphosphonate (5u) were
produced in 94% and 95% isolated yields, respective-
ly. Moreover, no cross-rearranged product was detect-
ed in the reaction by GC, GC-MS and 31P NMR anal-
ysis techniques. Therefore, we deduced that this type
Scheme 7. A plausible mechanism on the migration of phos-
phorus from oxygen to carbon atom.
of metalation-induced rearrangement occurred intra- erate the P-chirogenic phosphonates C with retention
molecularly rather than intermolecularly.
of the configuration at the phosphorus center.[11d]
Based on the present results, a possible mechanism Through the treatment of LDA, the ortho-proton of
is proposed in Scheme 7 for the lithium-induced rear- the aryl ring of P-chirogenic phosphonates C is lithiat-
rangement reaction. The starting material phenol A ed to form the metalation-induced intermediate D.
reacts with optically active H-phosphinates B to gen- The carbanion attacks the phosphorus atom and the
ArO undergoes an intramolecular collapse of phos-
phorus as a leaving group, generating the products E
and F with retention of the configuration at the phos-
phorus center.
Conclusions
In summary, we have developed a divergent method
for the preparation of P-chirogenic Rp- and Sp-(À)-
phosphoryl-substituted phenolic compounds by using
the optically active (Rp)-H-phosphinates as the effi-
cient phosphorylation reagents. It is noteworthy that
both of the reactions proceed in a highly stereospecif-
ic fashion with retention of the configuration at the
phosphorus atom, providing an efficient synthesis
method for a variety of optically active organophos-
phorus compounds from the easily available optically
active P(O)H compounds. Furthermore, we have fur-
Scheme 5. The stereospecific rearrangement reaction using
the diastereomeric H-phosphinate as the precusor.
Scheme 6. The cross-rearrangement reaction using two different types of phosphates.
Adv. Synth. Catal. 2014, 356, 781 – 794
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Biquan Xiong et al.
ing mixture was stirred at 808C for 14 h. Removal of the sol-
vent under a reduced pressure gave the crude product; pure
3a was obtained by passing the crude product through
a short silica gel column using hexane/EtOAc as eluent.
1H NMR (400 MHz, CDCl3, 258C, TMS): d=10.38 (s, 1H,
OH), 6.34–7.44 (m, 2H, Ar), 6.88–6.97 (m, 2H, Ar), 4.59–
4.67 (m, 2H, OCH), 1.39 (d, J=6.0 Hz, 6H, CH3), 1.21 (d,
ther clarified the mechanism of this type of metala-
tion-induced migration of phosphorus from oxygen to
carbon atom. This facile protocol will find wide appli-
cation in the construction of biologically active mole-
cules, catalyst ligands and organophosphorus materi-
als.
J=6.0 Hz, 6H, CH3); 13C NMR (100 MHz, CDCl3, 258C,
1
TMS): d=161.7 (d, 1J C,P =7.4 Hz, Ar), 134.9 (d, JC,P
=
=
=
1
2.4 Hz, Ar), 131.7 (d, 1JC,P =5.9 Hz, Ar), 119.4 (d, JC,P
Experimental Section
1
1
13.6 Hz, Ar), 117.5 (d, JC,P =12.0 Hz, Ar), 110.2 (d, JC,P
179.2 Hz, Ar C P), 71.7 (d, 1JC,P =4.9 Hz, OCH), 24.0 (d,
1JC,P =3.8 Hz, CH3), 23.6 (d, 1JC,P =5.2 Hz, CH3); 31P NMR
(160 MHz, CDCl3, 258C): d=20.4.
À À
General Remarks
All solvents used in reactions were freshly distilled. All
other reagents were recrystallized or distilled as necessary.
All reactions were performed under an atmosphere of dry
Typical Procedure for the Synthesis of Rp-5a
1
nitrogen. H (400 MHz), 13C (100 MHz), and 31P (162 MHz)
NMR spectra were recorded on a 400 MHz spectrometer in
To a solution of diisopropylamine (84 mL, 0.6 mmol) in THF
(1 mL) at À788C, 370 mL (0.6 mmol) of n-butyllithium were
added under an N2 atmosphere. The resulting mixture was
stirred at À788C for 30 min. Then, a degassed solution of P-
1
CDCl3. H NMR chemical shifts are reported using TMS as
internal standard; 13C NMR chemical shifts are reported rel-
ative to CDCl3 as internal standard. The electron ionization
method was used for the HR-MS measurement, and the
mass analyzer type is double-focusing.
chirogenic phosphonate 4a (0.5 mmol) in dry THFACHTUNGTRENNUNG(1 mL)
was slowly added at À788C and stirred for 1 h, and slowly
warmed to room temperature overnight. The reaction mix-
ture was concentrated under vacuum, and the crude materi-
al was purified by flash column chromatography (EtOAc/
hexane=1/10 to 1/5) to afford the P-chirogenic 2-hydroxy-
phenyl phenyl phosphinate (Rp-5a) as a white solid; isolated
yield: 96%; [a]2D6:3: +80.12 (c=0.986 in CHCl3). 1H NMR
(400 MHz, CDCl3, 258C, TMS): d 11.09 (s, 1H, OH), 7.80–
7.85 (m, 2H, Ar), 7.51–7.53 (m, 1H, Ar), 7.35–7.48 (m, 3H,
Ar), 7.17–7.23 (m, 1H, Ar), 6.92–6.95 (m, 1H, Ar), 6.81–
6.84 (m, 1H, Ar), 4.31–4.35 (m, 1H, OCH), 2.28–2.30 (m,
1H, CH), 1.70–1.72 (m, 1H, CH), 1.66–1.68 (m, 2H, CH2),
1.62–1.66 (m, 1H, CH), 1.14–1.20 (m, 2H, CH2), 0.99–1.03
(m, 2H, CH2), 0.97 (d, J=20.4 Hz, 3H, CH3), 0.82 (d, J=
3.6 Hz, 3H, CH3), 0.80 (d, J=3.2 Hz, 3H, CH3); 13C NMR
Typical Procedure for the Preparation of Optically
Pure H-Phosphinates (Rp)-2f[11]
The mixture of (l)-(À)-menthol (100 g, 641 mmol) and pyri-
dine (51.3 mL, 641 mmol) in Et2O (200 mL) was added
dropwise with stirring to a PhPCl2 (87.2 mL, 641 mmol) so-
lution in Et2O (400 mL) at 08C and then stirred at room
temperature overnight. Water (12 mL, 667 mmol) was
added, and the reaction mixture was washed with water and
extracted with hexane. The hexane layer was dried over
magnesium sulfate, filtered, and concentrated. Recrystalliza-
tion of the mixture in hexane (twice) at À308C gave pure
(Rp)-2f as white crystals (Rp/Sp>99/1); yield: 46%.
1
(100 MHz, CDCl3, 258C, TMS): d=162.5 (d, JC,P =4.7 Hz,
Ar), 134.6 (d, 1JC,P =1.9 Hz, Ar), 132.4 (s, Ar), 132.3 (d,
Preparation of H-Phosphinates (Rp)-2g[11]
1
1JC,P =9.5 Hz, Ar), 131.7 (d, JC,P =148.6 Hz, Ar-P), 131.2 (d,
1
1JC,P =10.5 Hz, Ar), 128.6 (d, JC,P=14.3 Hz, Ar), 119.2 (d,
PhCH2MgCl (1.0M in Et2O, 800 mL, 800 mmol) was added
dropwise to the Et2O (800 mL) solution of (À)-MenOPCl2
(206.4 g, 800 mmol) at 08C and then stirred at room temper-
ature overnight. Recrystallization of the mixture at À308C
gave pure (Rp)-2g as white needles (Rp/Sp>99/1); yield:
42%.
1JC,P =12.4 Hz, Ar), 117.9 (d, 1JC,P =9.6 Hz, Ar), 112.6 (d,
1JC,P =128.7 Hz, Ar P), 78.1 (d, 1JC,P =7.7 Hz, OCH), 48.9
(d, JC,P =4.7 Hz, CH), 42.8 (s, CH), 34.0 (s, CH2), 31.6 (s,
À
1
CH), 25.6 (s, CH2), 22.8 (s, CH2), 22.0 (s, CH3), 21.2 (s,
CH3), 15.6 (s, CH3); 31P NMR (160 MHz, CDCl3, 258C): d=
36.25; HR-MS: m/z=372.1829, calcd. for C22H29O3P:
372.1854.
Preparation of Optically Active (Rp)-Phosphonates
4[11d]
Crystallographic Data
The phenol (1 mmol) and an optically active H-phosphinate
(1 mmol) were dissolved in CCl4 (5 mL), Et3N (2 mmol) was
added under an N2 atmosphere, the resulting mixture was
stirred at room temperature for 16–24 h. Then the reaction
mixture was concentrated under vacuum, and the crude ma-
terial was purified by flash column chromatography
(EtOAc/Hexane=1/10 to 1/5) to afford the product.
CCDC 937532 (Sp-3n) and CCDC 902257 (Rp-5c) contain
the supplementary crystallographic data for this paper.
These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Typical Procedure for the Synthesis of 3a
Acknowledgements
To a mixture of 2-iodophenol (1 mmol), Cs2CO3 (1.5 mmol)
and CuI (0.1 mmol) in toluene, diisopropyl phosphonate
(1 mmol) was added under nitrogen atmosphere, the result-
This work was supported by NSFC (U1162109, 21273066,
21273067), Program for Changjiang Scholars and Innovative
792
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Research Team in University (IRT1238), the Program for
New Century Excellent Talents in Universities (NCET-10-
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ꢁ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2014, 356, 781 – 794