Diasteroselective addition of mono- and bis-silylphosphines to chiral aldehydes

Article abstract of DOI:10.1080/104265090921001

The addition of silylphosphines to chiral aldehydes proceeds with high diastereoselectivity to give optically pure tertiary α- trimethylsiloxyalkylphosphines. The diastereomeric excesses of the addition products were achieved to 90-100%. The reaction of b

Full text of DOI:10.1080/104265090921001

Phosphorus, Sulfur, and Silicon, 180:2335–2346, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/104265090921001
Diasteroselective Addition of Mono-
and Bis-Silylphosphines to Chiral Aldehydes
Anastasia O. Kolodiazhna
Irina V. Guliaiko
Oleg I. Kolodiazhnyi
National Academy of Sciences of Ukraine, Kiev, Ukraine
The addition of silylphosphines to chiral aldehydes proceeds with high
diastereoselectivity to give optically pure tertiary α-trimethylsiloxyalkylphosphines.
The diastereomeric excesses of the addition products were achieved to
90–100%. The reaction of bis(trimethylsilyl)phenylphosphine with the ace-
tonide of (R)-glyceraldehyde provides diastereomerically enriched tertiary
bis(glyceryl)phosphines.
Keywords Asymmetric induction; chiral aldehydes; chiral tertiary phosphines;
silylphosphines; stereoselectivity
INTRODUCTION
Chiral organophosphorus compounds are an important subject of inves-
tigation due to the widespread use of these compounds as ligands for
transition metal catalysis, biologically active substances, or drugs.1−3
The numerous patented chiral phosphines are proof of the interest in
such catalytic reactions from the industrial world.3,4 The preparation
of enantiomerically pure organophosphorus compounds is an impor-
tant and challenging area of contemporary synthetic organic chemistry.
Therefore the development of stereoselective methods for the synthe-
sis of organophosphorus compounds represents an important scientific
and applied problem.
Earlier we described a number of stereoselective methods for the
synthesis of chiral organophosphorus compounds.5−11 As part of our
Received July 29, 2004; accepted October 22, 2004.
Financial support for this work from the State Foundation of Basic Researches of
Ukraine (Project 03.07/00047) is gratefully acknowledged.
Address correspondence to Oleg I. Kolodiazhnyi, Institute of Bioorganic Chemistry,
National Academy of Sciences of Ukraine, Murmanskaya Street, 1, Kiev 02094, Ukraine.
E-mail: oikol123@bpci.kiev.ua
2335

2336
A. O. Kolodiazhna et al.
ongoing program directed towards developing new stereoselective re-
actions, we report the reaction of silylphosphines with chiral aldehydes
leading to the formation of optically active tertiary phosphines.
SCHEME 1
In contrast to the reaction of dialkylphosphites with aldehydes
(Abramov reaction, Scheme 1, eq. (a)), which was extensively studied,
the diastereoselective addition of silylphosphines to aldehydes was up
to now not reported (Scheme 1, eq. (b))1−4 although an achiral variant
of this reaction was formerly described.12−16
RESULTS AND DISCUSSION
The reaction of diphenyl(trimethylsilyl)phosphine with chiral aldehy-
des 1a–c resulted in the formation of products 3a–c in good yield and
high stereoselectivity (Scheme 2). The optical purity of a newly formed
α-carbon atom achieved 90–99% ee (Table I). The phosphines 3a–c are
colorless liquids and configurationally stable at room temperature. The
compounds 3a–c are hydrolytically stable, but are easily oxidized by
oxygen; therefore, all manipulations with these compounds have to be
performed in an inert atmosphere.
According to 31P NMR spectra, the compounds 3a–c containing two
asymmetric centers (α- carbon atom and R∗) were obtained as a mixture
of two diastereomers (Figure 1a). The chemical shifts δP–10– −4 ppm of
3a–c agree with the nature of the trivalent phosphorus atom. The big
differences between chemical shifts of two diastereomers attract special
attention.
SCHEME 2 Reaction of chiral aldehydes 1a–c with Ph2PH and Ph2PSiMe3.

Mono- and Bis-Silylphosphines
2337
TABLE I Stereoselectivity of Reaction Between Ph2PSiMe3 and
Aldehydes 1a–c
Entry
1
Compound
R
Solvent
THF
to(◦C)
Yield, %
85
dra
3a
−20
95:5
2
3
3b
3c
Toluene
Toluene
−20–0
90
60
∼100:0
−20–+20
90:10
aDiastereomeric ratio (dr) was determined by NMR spectra.
To elucidate the effect of the Me3Si group, we have examined the
reaction of diphenylphosphine with chiral aldehydes 1a–c and found
that this reaction is reversible and proceeds with low stereoselectivity
to give a mixture of the initial compounds and the addition product 2a
with dr 45:55 (Schme 2). The 31P NMR spectra of this reaction mixture
show the signals −8.30 and −10.09 ppm (diastereomers of 2a) and the
signal −40.7 ppm (diphenylphosphine) (Figure 1b).
We concluded that the reaction of silylphosphines with aldehy-
des is kinetically controlled, unlike the reaction of diphenylphosphine
with aldehydes 1a–c which is probably thermodynamically controlled,
FIGURE 1 31P NMR spectrum of crude reaction mixtures of 2a (a) and 3a (b).

2338
A. O. Kolodiazhna et al.
because the adducts 2a–c dissociate with the formation of initial com-
pounds and easily racemize.
Compounds 3a–c react with borane in THF solution and were trans-
formed into borane complexes 4a–c, which were purified by column
chromatography on silica gel. Structure and purity of the borane
complexes 4a–c were confirmed by nuclear magnetic resonance and
elemental analysis.
The 31P NMR signals of the borane complexes are observed at
+20–+30 ppm and have the typical shape of broad multiplets resulting
from phosphorus-boron coupling that enable easy monitoring of these
1
compounds.17−20 The H NMR spectra show the signals of all hydro-
gen atoms in the molecule, without any doubling caused through the
presence of diastereomers.
Borane-phosphine complexes 4a–c are configurationally stable at
room temperature. They are also hydrolytically stable and are not oxi-
dized by oxygen of the air.
Decomplexation of the compounds 4a–c with a large excess of an
amine such as diethylamine led to the formation of chemically and
stereochemically pure tertiary phosphines 3a–c (Table II). The reaction
proceeds slowly and is completed at room temperature over a period of
16 h. The BH3-part of the phosphine-borane complex was removed on
treatment with a large excess of an amine such as diethylamine. The
identity of the purified (R,S)-diastereomer 3a, and the major diastere-
omer of the initial diastereomeric mixture of the tertiary phosphine
(R,S)-3a and (S,S)-3a, was confirmed by 31P NMR spectra of the mix-
ture of these two products.
The oxidation of the compounds 3a–c by oxygen of the air provides
the phosphine oxides 5a–c in high yield (∼90%) (method a, Table II). The
TABLE II Synthesis of Tertiary Phosphine Oxides 5a–c
Yield (%)
dea (%)
Yield (%)
dea (%)
Entry
Compound
(Method a)
(Method a)
(Method b)
(Method b)
1
2
3
5a
5b
5c
90
50
40
95
98
98
60
70
40
75
80
70
ade = diastereomeric excess.

Mono- and Bis-Silylphosphines
2339
SCHEME 3 Reaction of the aldehyde 1a with the phenyl-bis(trimethylsilyl)-
phosphine.
compounds 5a–c were isolated as colorless crystalline substances; the
structure and purity were confirmed by elemental analysis and spec-
troscopic studies. To additionally confirm the structure of compounds
5a–c we have prepared them also by an alternative reaction between
diphenylphosphine oxide and aldehydes 1a–c (method b, Table II). We
have found that this reaction proceeds with moderate stereoselectiv-
ity (∼75% de); however, the crystallization of additional products in
toluene provides the optically pure compounds 5a–c, which are identi-
cal to compounds 5a–c prepared by method a.
The reaction of bis(trimethylsilyl)phenylphosphine with aldehyde 1a
proceeds as well with good stereoselectivity. The product 6 contains four
chiral atoms and can exist as a mixture of several diastereomers, but the
reaction led to the formation of one predominantly diastereomer. The
subsequent treatment of the compound 6 with borane resulted in the op-
tically pure borane complex 7, which constitutes a new chiral ligand.21
The compound 7 is stable to oxidation and hydrolysis by air, can be kept
without racemisation, and can be purified by column chromatography
on Silica Gel. The BH3-part of the phosphine-borane complex 7 was re-
moved on treatment with diethylamine to give the diastereomerically
pure tertiary phosphine 6. The compound 6 was oxidized to the corre-
sponding tertiary phosphine oxide 8, which was isolated as a crystalline
product. The structure, chemical, and optical purity of compounds 6–8
have been confirmed by elemental analysis, NMR spectra, and HPLC.
We have also used derivatization with dimenthylchlorophosphite and
Mosher acid.22
The newly formed asymmetric center of the compounds 3–5, evi-
dently, is of the (S)-configuration, as was found on the basis of NMR
spectra: The big value of the 3 J constant and small value of the 2 J
HH
HP
H
constant of compounds 3–5 show the anti-conformation of H C1 C2

2340
A. O. Kolodiazhna et al.
FIGURE 2 The 31P NMR spectra of the borane complex 4a.
and O P C1 H bonds.23 The stereochemistry of this reactions prob-
ably is kinetically controlled. Therefore the nucleophilic attack of
silylphosphines to the less shielded (Si) face of the carbonyl group
provides preferentially the (S)-3 diastereomer according to the Cram’s
rule. Consideration of the stereochemical model of the formed products
showed that the stereochemistry of the phosphaaldol reaction is in the
agreement with Cram’s rule (Figure 3).24
FIGURE 3 Stereochemical Cram model of the reaction between the aldehyde
1a and Ph2PSiMe3.

Mono- and Bis-Silylphosphines
2341
CONCLUSION
In conclusion, we have found that the reaction between silylphosphines
and chiral aldehydes proceeds with good stereoselectivity to give chiral
tertiary phosphines in high chemical yields. The reaction can be applied
for asymmetric synthesis of new chiral organophosphorus compounds,
including organophosphorus ligands or bioactive substances.
EXPERIMENTAL
Melting points are uncorrected. The NMR spectra were recorded on a
1
Varian VXR-300 spectrometer at 300 (1H) and 126.16 MHz (31P). H
chemical shifts are given in δ (ppm) relative to Me4Si as internal stan-
dard. 31P NMR spectra were recorded relative to 85% H3PO4 as an
external standard. All manipulations were carried out in an argon at-
mosphere. The following solvents were distilled in an inert atmosphere:
diethyl ether, hexane, heptane, benzene, CCl4 (over P4O10), methanol,
triethylamine (over sodium), and ethyl acetate (over CaCl2). Column
chromatography was performed using silica gel 60 (Fluka). Optical ro-
tations of the compounds were determined on a Polax-2L polarimeter
in solvents, which were purified by standard methods. Optically active
reagents were obtained from Aldrich and Fluka and were used with-
out special purification. Silylphosphines were prepared according to the
procedure which we described earlier.25
2,2-Dimethyl-1,3-dioxolan-4-yl-trimethylsiloxymethyl-
diphenylphosphine (3a)
To a solution of 1a (1.1 mmol) 5 mL of toluene was added to Ph2PSiMe3
(1.0 mmol) at −20◦C. The reaction mixture was allowed to stand at
this temperature overnight. The temperature was raised to +20◦C and
in 1 h the solvent was evaporated to give tertiary phosphine 3a. The
product was obtained as a colorless liquid.
To a solution of 3a in THF (3 mL) a solution of 0.12 mmol of borane
in THF (1.1 mmol) was added dropwise with stirring at −20◦C and the
reaction mixture was allowed to stand at room temperature. After 6 h
the solvent was removed in vacuo and the residue was chromatographed
on a column with silica gel with hexane-ethyl acetate (6:1) as an eluent
to give the borane complex 4a.
Yield 80%. Rf 0.3 (hexane-ethyl acetate = 3:1). [α]D + 41.6 (c 1.5, ethyl
acetate).
Anal. calcd. for C21H32BO3PSi:P, 7.70; Found: P, 7.55.

2342
A. O. Kolodiazhna et al.
1H NMR (CDCl3), δ, ppm (J, Hz): −0.16 s (SiMe3); 0.18–1.4 m (BH3);
1.25 s; 1.33 s [(CH3)2C]; 3.23 dd J 8, J 1; 3.43 dd J 7.5, J 1 (CH2O); 4.53
m (CHCH2O); 5 dd J 4.5, J < 1 (PCH); 7.66 m; 7.93 m (C6H5).
31P NMR (CHCl3): δP 21.6 ppm, d J 57 Hz.
PB
The borane complex 4a was dissolved in excess diethylamine and
kept under argon for 16 h. Excess diethylamine was removed in vacuo,
and residue was extracted with hexane, which was filtered under argon
to leave the optically pure tertiary phosphine 3a. The 31P NMR spec-
trum showed only one signal due to the (SR)-diastereomer (confirmed
by mixed testing with an authentic diastereomer).
Yield 90%, [α]2D0–7 (c 4, toluene).
NMR 1H (CDCl3), δ, ppm (J, Hz): −0.02 s (CH3Si); 1.33 s (CH3); 4.33
m; 4.49 (OCH2CH); 4.72 m (CH2CHO); 4.99 m (PCH); 7.5 m; 7.9 m
(C6H5).
31P NMR (CHCl3): δ −7.69; −10.62 ppm (ratio ∼11:1).
Trimethylsiloxy (2,2,7,7-Tetramethylperhydrodi[1,3]dioxolo-
[4,5-b:4,5-d]pyran-5-yl)methyl-diphenylphosphine (3b)
A solution of aldehyde 1b (0.01 mol) in toluene was added to a solution
of diphenyl trimethylsilylphosphine (0.01 mol) in toluene at 0◦C and the
reaction mixture was left for 2 h at this temperature. The solvent was
removed under pressure and reduced. Yield 80%. 31P NMR (toluene),
ppm: δP 4.4.
To a solution of phosphine 3b in 5 mL of THF a solution of borane
(0.012 mol) in THF was added dropwise with stirring and the reac-
tion mixture was allowed to stand at room temperature for 12 h. The
solvent was removed in vacuo and the residue was chromatographed
on a column with silica gel (3:1 hexane-ethyl acetate as eluent). The
diastereomeric excesses and yields are collected in Table I.
Rf 0,35. [α]D −71.8 (c 3, CHCl3).
1H NMR (CDCl3), δ, ppm (J, Hz): −0.18 c (9H, CH3Si); 0.8–1.6 m
(3H, BH3); 1.13 s (3H, CH3); 1.18 s (3H. CH3); 1.27 s (3H. CH3); 1.48 s
(3H. CH3); 3.99 ddd (1H, PCCH,JPH 7; JHH 7, JHH 9); 4.16 dd (1H, PCH,
J
J
HH
3, J 5.1); 4.21 dd (1H, CH, J 8, J 1) 4.53 dd (1H, CH, J 9,
1.2); 4.94 dd (1H, PCH, J 9, J 1.5); 5.29 d (1H, CH, J 5.4);
HH HP HH
HH
HH HH HH HH
7.4 m; 8.0 m (10H, C6H5).
31P NMR (CDCl3): δ 25.3 ppm, m.
The borane complex 4b was dissolved in 5 mL of diethylamine and
left for 12 h. The solvent was removed in vacuo to give the tertiary phos-
phine 3b as a diastereoisomerically pure, easily oxidized liquid. The 31
P
NMR spectrum showed only one signal due to the (SR)-diastereomer
3a (confirmed by mixed testing with an authentic diastereomer).
31P NMR (CDCl3): δ 4.4 ppm.

Mono- and Bis-Silylphosphines
2343
N,N-Dibenzyl-1-trimethylsiloxy-2-pentanamine-methyl-
diphenylphosphine (3c)
The product 3c and its borane complex 4c were prepared analo-
gously to compounds 3a, 4a. The diastereomeric excesses and yields
are collected in Table I. The product was prepared in spectroscop-
ically pure state and used for further conversions without special
purification.
31P NMR (toluene): δ −10.5; −11.3 ppm (ratio 9:1).
Borane complex (4c): Yield 64%. Rf 0,35, [α]D −71.8 (c 3, CHCl3).
Anal. calcd. for C35H37BNOPSi: P, 5.46; Found: 5.30.
31P NMR (CHCl3) δ, ppm (J, Hz): δ 25.3, m, 1 J 57.
PB
2,2-Dimethyl-1,3-dioxolan-4-yl-trimethylsiloxymethyl-
diphenylphosphine Oxide (5a)
Method a
The compound 3a was dissolved in toluene and left for 12 h in the air.
As a result a solid product was obtained. This product was dissolved in
toluene and was left to crystallize. The crystalline product was filtered
to provide the pure diastereomer 5a.
Mp 167◦C, [α]D20+11 (CHCl3, c 2).
Method b
To a solution of diphenylphosphine oxide (0.01 mol) of 5 mL of
toluene a solution of aldehyde (1a) (0.011 mol) and diazabicycloun-
decene (0.001 mol) in 3 mL of toluene was added with cooling.
The reaction mixture was left for 6 h at 0◦C. The solvent was re-
moved in vacuum. The 31P NMR spectrum showed the presence of
(1S, 2R)- and (1R, 2R)-diastereomers. 31P NMR (CHCl3): δ 30.87 and
29.45 ppm.
The residue was obtained as a viscous liquid to which toluene
was added and left to crystallize. The next day the crystalline prod-
uct was filtered off and was recrystallized from toluene. The mother
liquor was evaporated. The residue, enriched in the minor diastere-
omer, was separated by column chromatography with silica gel (CHCl3-
ethylacetate 1:1). The diastereomeric excesses and yields are col-
lected in Table II. Anti-diastereomer. M.p. 167◦C, [α]D20 = +11 (c 2,
CHCl3).
NMR 1H (CDCl3), δ, ppm (J, Hz): 1.17 s (Me2Ca); 1.20 s (Me2Cb); 3.88
d J 2 (CaH2); 3.897 d J 1.5 (CbH2); 4.39 dt J 6.5, J 2 (OCHCH2); 4.59
dd J 5, J 0.9 (PCH); 4.4 m (OH); 7.8 m, 4H; 7.49 m (6H).
NMR 31P (CHCl3): δ 30.87 ppm.
Cis- diastereomer. Rf 0.2.

2344
A. O. Kolodiazhna et al.
1H NMR (CDCl3) 1.14 s [(CH3)2Ca]; 1.23 s [(CH3)2Cb]; 3.992 s; 3.902 s
(CH2); 4.39 dt J 6.5, J 2 (OCHCH2); 4.4 br (OH); 4.59 dd J 5, J 5 Hz
HP
(PCH); 7.8 m, 4H; 7.49 m (6H).
NMR 31P (CHCl3): δ 29.45 ppm.
Anal. calcd. for C18H21O4P:P, 9.32; Found: 9.55.
1-Hydroxy-[(2,2,7,7-tetramethylperhydrodi[1,3]dioxolo[4,5-
b:4,5-d]pyran-5-yl]-methyl Diphenylphosphine Oxide (5b)
The compound 5b was prepared analogously to 5a. The diastereomeric
excess and yield are collected in Table II.
m.p. 156◦C, [α]D20 −59 (c 3, CHCl3).26
Anal. calcd. for C24H29O7P: P, 6.73; Found: 6.54.
NMR 1H (CDCl3), δ, ppm (J, Hz): 1.11 s (3H, CH3); 1.18 s (3H, CH3);
1.31 s (3H, CH3); 1.32 s (3H, CH3); 4.02 dd (1H, CH, J 2.1; J 5);
HH
PH
4.22 ddd (1H, PCCH, J 2.0, J 7, J 8); 4.43 dd (1H, CH, J 8,
HH
HH
HH
HH
J
HH
1.5); 4.58 dd (1H, CH, J 8, J 1); 4.63 dd (1H, PCH, J 3, J
HH HH HP HH
8); 5.07 d (1H, CH, J 5); 6.14 br (1H, OH); 7.3 m; 7.8 m (10H, C6H5).
HH
31P NMR (CHCl3): δ 32.2 ppm.
N,N-Dibenzyl-1-hydroxy-2-pentanamine-methyl-
diphenylphosphine Oxide (5c)
The compound 5c was prepared analogously to 5a. The diastereomeric
excess and yield are collected in Table II.
m.p. 121◦C, [α]D20 = −30 (CHCl3, c 2).
Anal. calcd. for C35H44NO2PSi: P, 5.44; Found: 5.41.
1H NMR (CDCl3): 0.11, d J 6.6 [(CH3)2CH]; 0.84, d J 6.6 [(CH3)2CH];
1.23 m (CH2); 1.83 m (CH2); 2.84 m (CH); 3.35 s; 4.0 s; 3.88 s; 3.93 s
(CH2N); 4.42 m (OH); 4.82 dd J 1, J 1 (PCH); 7–7.8 m (C6H5).
NMR 31P (CHCl3): δ 29.4 ppm.
Bis[2,2-Dimethyl-1,3-dioxolan-4-yl(trimethylsiloxy)-
methyl]phenylphosphine (6)
(a) Preparation of Borane Complex (7)
To a solution of 1a (2.2 mmol) 5 mL of toluene was added slowly
to PhP(SiMe3)2 (1.0 mmol) while cooling. The solution was left at this
temperature overnight. The temperature was raised to +20◦C and in
1 h the solvent was evaporated to give tertiary phosphine 6.
NMR 31P (CHCl3): δ −10.68 ppm.
Then to a solution of 6 in THF (3 mL) a solution of borane (1.1 mmol)
in THF was added dropwise with stirring at −20◦C. The reaction

Mono- and Bis-Silylphosphines
2345
mixture was allowed to stand at room temperature. After 6 h the sol-
vent was removed in vacuo to give tertiary phosphine 6 and the residue
was chromatographed on column with silica gel, using a mixture of
hexane-ethyl acetate (6:1) as eluent.
Yield 70%. Rf 0.37 (hexane-ethyl acetate 6:1). [α]2D0 = +23.6 (c 3,
CHCl3).
Anal. calcd. for C24H46BO6PSi2: P, 5.86; Found: P, 5.66.
1
NMR H (CDCl3), δ, ppm: −0.17 s (SiMe3); −0.20 s (SiMe3); 0.6–
1.3 m (BH3); 1.11 s; 1.20 s; 1.33 s; 1.36 s [(CH3)2C]; 4.59 m; 4.53 m
(CHCHCH2); 3.64 dt; 3.77 dt; 3.9 dt; 4.11 dt (OCH2); 5.16 dd J 9, J <1
(PCH); 7.2 m; 7.8 m (C6H5).
NMR 31P (CHCl3): δ 27.4 ppm.
(b) Decomplexation of Borane Complex ( 7)
The borane complex 7 was dissolved in excess diethylamine and
the mixture was kept under argon for 12 h. Then volatile matter was
evaporated in vacuum and the residue was extracted with hexane,
which was filtered under argon to give spectroscopically pure tertiary
phosphine 6.
Yield 90%, colorless easily oxidable liquid, [α]2D0 = −12.5 (c 3, ethyl
acetate). NMR 31P (CHCl3): δ −10.68 ppm.
Bis(2,2-Dimethyl-1,3-dioxolan-4-yl-hydroxymethyl)-
phenylphosphine Oxide (8)
The compound 8 was prepared analogously to 5a. Rf 0.25 (hexane-ethyl
acetate 2:1). Anal. calcd. for C18H27O7P: P, 8.02; Found: P, 7.86.
NMR 31P (CHCl3): δ 43 ppm.
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