Stable Optically Pure Phosphino(silyl)carbenes: Reagents for Highly Enantioselective Cyclopropanation Reactions

Article abstract of DOI:10.1002/chem.200305722

The stability of phosphino(trimethylsilyl)carbenes bearing cyclic diamino substituents on phosphorus is strongly dependent on the steric hindrance of the nitrogen substituents. Phosphinocarbenes 3 and 7, derived from the trans-N,N′-diisopropylcyclohexane-

Full text of DOI:10.1002/chem.200305722

FULL PAPER
Stable Optically Pure Phosphino(silyl)carbenes: Reagents for Highly
Enantioselective Cyclopropanation Reactions
Jerzy Krysiak,[a, b] Cÿline Lyon,[a] Antoine Baceiredo,*[a] Heinz Gornitzka,[a]
Marian Mikolajczyk,*[b] and Guy Bertrand*[a, c]
Abstract: The stability of phosphino(-
trimethylsilyl)carbenes bearing cyclic
diamino substituents on phosphorus is
strongly dependent on the steric hin-
drance of the nitrogen substituents.
Phosphinocarbenes 3 and 7, derived
from the trans-N,N’-diisopropylcyclo-
hexane-1,2-diamine and N,N’-diiso-
propyl-1,2-ethanediamine, are not ob-
served; instead the 1,3-diphosphete 4
and a novel six-membered heterocycle
8, which results from the dimerization
of 3 and the reaction of 7 with its diazo
precursor 6, respectively, have been
isolated. In contrast, the phosphino(si-
lyl)carbene 14 derived from N,N’-di-
tert-butyl-1,2-ethanediamine has been
isolated in high yield. By using the
enantiomerically pure (S,S)-, and
(R,R)-N,N’-di-tert-butyl-1,2-diphenyl-
1,2-ethanediamines, the first optically
pure phosphino(sily)carbenes (S,S)-17
and (R,R)-17 have been prepared.
They react with methyl acrylate to give
the
corresponding
cyclopropanes
Keywords: asymmetric synthesis ¥
(S,S,R,R)-19 and (R,R,S,S)-19 with a
total syn diastereoselectivity and an ex-
cellent enantioselectivity (de>98%).
carbenes
¥ cycloaddition ¥ diazo
compounds ¥ phosphorus
Introduction
thesis of the first stable, optically active phosphino(silyl)car-
benes, and subsequent highly selective cyclopropanation
reactions.
The presence of cyclopropane subunits in many natural and
synthetic biologically active compounds,[1] as well as the util-
ity of these small rings as synthetic intermediates,[2] has pro-
moted many strategies for their construction. We have pre-
viously demonstrated that, in contrast to the other known
stable carbenes, namely aminocarbenes,[3,4] singlet nucleo-
philic phosphino(silyl)carbenes are efficient building blocks
for the preparation of cyclopropanes.[5] Notably, reaction
with monosubstituted olefins affords three-membered rings
with a total syn diastereoselectivity (with respect to the
phosphino group).[5b] With olefins bearing a chiral auxiliary,
asymmetric inductions up to 87% de were observed, al-
though with low chemical yields.[5c] Here we report the syn-
Results and Discussion
Phosphino(silyl)carbenes are best described as phosphorus
vinyl ylides with a planar phosphorus atom,[6] and only those
bearing amino substituents at phosphorus are stable.[4d]
Therefore, the obvious way to introduce chirality was to use
a cyclic diamino C2-symmetric system at phosphorus. To
evaluate the stability of this type of phosphino(silyl)carbene,
racemic or achiral diamines were first used. With the (Æ)-
trans-N,N’-diisopropylcyclohexane-1,2-diamine,[7a] the diazo
compound 2 was obtained in near quantitative yield as a
yellow oil (Scheme 1). Attempts to prepare the correspond-
ing carbene 3 by photolysis of 2 at À408C gave the hetero-
cycle 4. This 1,3-diphosphete,[8] which is formally the head-
to-tail [2+2] dimer of carbene 3, has been fully character-
ized; the results of the X-ray diffraction study of 4 are given
in Figure 1.
Since, the [bis(diisopropylamino)phosphino](trimethylsi-
lyl)carbene is stable at ambient temperature and shows no
tendency for dimerization, the instability of carbene 3 was
rather surprising, and could be due to the strained bicyclic
structure introduced by the diaminocyclohexane ligand. To
check this hypothesis we prepared the phosphino(trimethyl-
silyl)diazomethane 6 derived from the achiral N,N’-diiso-
[a] J. Krysiak, C. Lyon, Dr. A. Baceiredo, Dr. H. Gornitzka,
Prof. G. Bertrand
Laboratoire Hÿtÿrochimie Fondamentale et Appliquÿe (UMR 5069)
Universitÿ Paul Sabatier, 118, route de Narbonne
31062 Toulouse Cedex 04 (France)
[b] J. Krysiak, Prof. M. Mikolajczyk
Centre of Molecular and Macromolecular Studies
Polish Academy of Sciences, Departement of Heteroorganic Chemis-
try, Sienkiewicza
112, 90 363 Lodz (Poland)
[c] Prof. G. Bertrand
UCR-CNRS Joint Research Chemistry Laboratory (UMR 2282)
Department of Chemistry, University of California
Riverside, CA 92521 0403(USA)
1982
¹ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/chem.200305722
Chem. Eur. J. 2004, 10, 1982 1986

1982 1986
Scheme 1. R=SiMe3.
Figure 1. Structure of 1,3-diphosphete 4 (thermal ellipsoids drawn at
50% probability for non-hydrogen atoms; hydrogen atoms omitted for
clarity).
Figure 2. Strcture of six-membered heterocycle
drawn at 50% probability for non-hydrogen atoms; hydrogen atoms
omitted for clarity).
8
(thermal ellipsoids
propyl-1,2-ethanediamine.[7b] Photolysis of 6 in solution in
pentane at À808C afforded the six-membered heterocycle 8
in near quantitative yield (Scheme 2). The presence of two
nonequivalent phosphorus atoms was indicated by an AX
system in the 31P NMR spectrum [d=26.7 and 36.3 ppm,
sis, we conducted the photolysis of 6 in the presence of the
phosphine 9. In this case, the formation of 8 was avoided,
and phosphorus ylide 10 was isolated (Scheme 3). The cou-
pling of the phosphine with the carbene center was indicat-
ed by an AX system in the 31P NMR spectrum [d=54.2 and
Scheme 2. R=SiMe3.
Scheme 3.
J(P,P)=34 Hz]. The heterocyclic structure of 8 was unam-
biguously established by a single-crystal X-ray diffraction
study (Figure 2). Interestingly, compound 8, which presents
an endocyclic phosphazine unit, is perfectly stable at room
temperature. There was no evidence for the release of dini-
trogen to afford the corresponding 1,3-diphosphete.
The formation of 8 probably results from the reaction of
the transient carbene 7 with the starting diazo compound 6.
One can imagine the interaction of the carbene center of 7
with the phosphine center of 6,[9] followed by an intramolec-
ular Staudinger Meyer reaction.[10] To validate this hypothe-
127.7 ppm, J(P,P)=147 Hz]. Interestingly, transient carbene
7 can also be trapped by tert-butyl isocyanide, which affords
the corresponding phosphinoketeneimine 11 in good yield
[IR: n˜ =1979 (n(CCN)) cmÀ1]. However, no cyclopropana-
tion reactions occurred in the presence of either electron-
poor or electron-rich olefins; only the formation of 8 was
observed.
These results clearly demonstrate that the stability of
phosphino(silyl)carbenes is dramatically related to the steric
bulk of the amino substituents at phosphorus. To confirm
this, the five-membered ring skeleton was kept unchanged,
1983
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A. Baceiredo, M. Mikolajczyk, G. Bertrand et al.
FULL PAPER
while the isopropyl groups on nitrogen were replaced by
tert-butyl substituents. In this case, the corresponding car-
bene 14 appeared to be perfectly stable at room tempera-
ture and could be isolated in near quantitative yield
(Scheme 4).
Scheme 4.
Figure 3. Strcture of (SSRR)-19 (thermal ellipsoids drawn at 50% proba-
Taking these results into account, the (S,S)-, and (R,R)-
bility for non-hydrogen atoms; hydrogen atoms omitted for clarity).
N,N’-di-tert-butyl-1,2-diphenyl-1,2-ethanediamines[7c]
were
used to prepare the corresponding enantiomerically pure
phosphino(silyl)diazo compounds (S,S)-16 and (R,R)-16, re-
spectively. Both enantiomers have been isolated in good
yields as yellow oils [d(P)=116.3ppm; IR: n˜ =2018
(n(CN2)) cmÀ1]. The photolysis of solutions of (S,S)-16 and
(R,R)-16 in toluene at À408C gave, after evolution of dini-
trogen, the corresponding stable optically pure carbene
(S,S)-17 and (R,R)-17, respectively. The reactions were
monitored by 31P NMR spectroscopy (d=À32.7 ppm) and
were complete after 18 h (Scheme 5).
Figure 4. Structure of (RRSS)-19 (thermal ellipsoids drawn at 50% prob-
ability for non-hydrogen atoms; hydrogen atoms omitted for clarity).
Scheme 5.
Addition of two equivalents of methyl acrylate to a solu-
tion of each enantiomer of carbene 17 in toluene cleanly
yields the corresponding cyclopropanes 18. According to 31P
and 1H NMR spectrocospy, prior to any purification, only
one diastereomer could be detected in each experiment
(de>98%). After addition of elemental sulfur the corre-
sponding thioxo derivatives (S,S,R,R)-19 (aD =+19.2) and
(R,R,S,S)-19 (aD =À19.2) were isolated as colorless crystal-
line solids in 85 and 80% yield, respectively (Scheme 6).
The syn-selectivity has already been rationalized by in-
voking a second-order orbital interaction between the phos-
phorus center and the olefin substituent.[5b] The very high
enantioselectivity observed is a consequence of the obstruc-
tion of one side of the phosphino(silyl)carbene by one of
the phenyl groups, directing the approach of the olefin as in-
dicated in Scheme 7.
Scheme 6.
The absolute configuration of the two newly formed chiral
centers and the total syn diastereoselectivity (with respect to
the phosphino group) were confirmed by two X-ray diffrac-
tion studies (Figure 3and Figure 4).
Scheme 7.
1984
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Chem. Eur. J. 2004, 10, 1982 1986

Stable Optically Pure Phosphino(silyl)carbenes
1982 1986
1
3J(P,C) =11.8 Hz; CCH3), 30.3 (d, 3J(P,C) =11.9 Hz; CCH3), 32.8 (d, J(P,C)
=
Conclusion
56.1 Hz; PC), 54.8 (s; PNC), 56.1 (d, 2J(P,C) =24.8 Hz; PNC), 73.6 (d,
2J(P,C) =10.1 Hz; NCH), 74.4 (d, 2J(P,C) =7.3Hz; NCH), 127.7, 128.0, 128.5,
144.6 ppm (s; Caro).
In conclusion, we have presented the synthesis of the first
stable optically pure phosphino(silyl)carbenes. They under-
go highly stereoselective cyclopropanation reactions: total
syn diastereoselectivity (with respect to the phosphino
group), and de>98%. The possible cleavage of the chiral
auxiliary, as well as the enantioselective synthesis of oxir-
anes[11] are under investigations.
General procedure for the photolysis of diazophosphines 2, 6, 13, and 16:
A solution of diazophosphine (0.3mmol) in toluene or pentane (2 mL)
was irradiated (lmax =312 nm) at À408C. The evolution of the reaction
was monitored by 31P NMR spectroscopy.
Synthesis of four-membered ring 4: After irradiation overnight, heterocy-
cle 4 slowly crystallized in the toluene solution at À408C as white crystals
(75%). m.p. 2508C (decomp); 31P{1H} NMR (CDCl3): d=48.8 ppm;
1H NMR (CDCl3): d=0.28 (s, 9H; CH3Si), 0.32 (s, 9H; CH3Si), 1.30 (d,
3J(H,H) =6.9 Hz, 12H; CH3), 1.34 (d, 3J(H,H) =6.9 Hz, 12H; CH3), 1.00 1.47
(m, 8H; CH2), 2.10 (m, 8H; CH2), 2.79 (m, 4H; CH), 4.14 ppm (sept,
Experimental Section
3J(H,H) =6.9 Hz, 4H; CHN); 13C{1H} NMR (CDCl3): d=1.3(s; CH Si), 4.0
3
2
(s; CH3Si), 19.3and 25.7 (s; CH ), 24.4 and 32.8 (s; CH2), 43.9 (d, J(P,C)
=
3
2
General remarks: All manipulations were performed under an inert at-
mosphere of argon using standard Schlenk techniques. Dry, oxygen-free
solvents were employed. 1H, 13C, and 31P NMR spectra were recorded on
Bruker AC80, AC200, WM250, or AMX400 spectrometers. 1H and 13C
chemical shifts are reported in ppm relative to Me4Si as external stan-
dard. 31P NMR downfield chemical shifts are expressed with a positive
sign, in ppm, relative to external standards of 85% H3PO4. Infrared spec-
tra were recorded on a Perkin-Elmer FT-IR Spectrometer 1600.
21.6 Hz; CHN), 60.1 ppm (d, J(P,C) =20.4 Hz; CHN).
Synthesis of six-membered heterocycle 8: After irradiation overnight,
heterocycle 8 slowly crystallized in the toluene solution at À408C as
white crystals (80%). m.p. 162 1638C; 31P{1H} NMR (CDCl3): d=26.7
and 36.3 ppm (d, J(P,P) =33.6 Hz); 1H NMR (CDCl3): d=0.12 (s, 9H;
CH3Si), 0.16 (s, 9H; CH3Si), 1.14 (m, 24H; CH3C), 3.13 (m, 8H; CH2),
3.40 ppm (m, 4H; CH); 13C{1H} NMR (CDCl3): d=0.8 (s; CH3Si), 3.0 (s;
CH3Si), 20.2 21.9 (m; CH3C), 37.1 (d, 2J(P,C) =9.2 Hz; CH2), 38.0 (d,
2
2J(P,C) =8.3Hz; CH 2), 43.4 (d, 2J(P,C) =9.2 Hz; CH), 43.9 ppm (d, J(P,C)
=
General procedure for the synthesis of chlorophosphines 1, 5, 12, and 15:
One equivalent of PCl3 (18 mmol) was added dropwise at 08C to a solu-
tion of diamine (18 mmol) and Et3N (55 mmol) in toluene (30 mL). The
reaction mixture was warmed to room temperature, and stirred for 2 h.
After removal of ammonium salts by filtration, the solvent was removed
under vacuum, and the chlorophosphines were obtained in near quantita-
tive yields as colorless oils. Spectroscopic data for 1,[12a] 5,[12b] and 12[12c]
are in agreement with those previously described.
15: (S,S)-15, [a]2D0 =À25.4; (R,R)-15, [a]D20 =+25.4 (c=0.05 in CH2Cl2);
31P{1H} NMR (C6D6): d=176.0 ppm; 1H NMR (C6D6): d=1.25 (s, 18H;
CH3C), 4.52 (d, 3J(P, H ) =6.1 Hz, 2H; CHNP), 7.32 ppm (m, 10H; Haro);
13C{1H} NMR (CDCl3): d=30.5 (d, 3J(P, C) =11.9 Hz, CCH3), 55.1 (d,
2J(P, C) =12.0 Hz; PNC), 75.0 (d, 2J(P, C) =11.1 Hz; NCH), 127.4, 127.8,
128.7, 143.6 ppm (s; Caro).
6.4 Hz, CH); elemental analysis calcd (%) for C24H54N6Si2P2: C 52.91, H
9.99, N 15.42; found: C 52.95, H 10.05, N 15.36.
Synthesis of phosphine 9: Methyllithium (3.5 mL, 5.0 mmol; 1.3 equiv)
was added dropwise at À788C to a solution of chlorophosphine 5 (0.82 g,
4.0 mmol) in THF (10 mL). The reaction mixture was warmed to room
temperature, and stirred for 1 h. The solvent was removed under
vacuum, and the residue was extracted with pentane (2î5 mL). Phos-
phine 9 was obtained as a colorless oil, after evaporation of pentane
(0.76 g, 88%). 31P{1H} NMR (CDCl3): d=95.3ppm.
Synthesis of phosphorus ylide 10: After irradiation of 6 overnight in the
presence of 1.3equivalents of phosphine 9, 31P NMR spectroscopy indi-
cated the quantitative formation of ylide 10, which was obtained as a
yellow oil, after evaporation of pentane. 31P{1H} NMR (C6D6): d=54.2
and 127.7 ppm (d, J(P,P) =146.5 Hz); 1H NMR (C6D6): d=0.49 (s, 9H;
CH3Si), 0.89 (d, 3J(H,H) =6.6 Hz, 6H; CH3C), 1.05 (d, 3J(H,H) =6.7 Hz, 6H;
CH3C), 1.28 (d, 3J(H,H) =7.6 Hz, 6H; CH3C), 1.32 (d, 3J(H,H) =6.9 Hz, 6H;
CH3C), 1.67 (dd, J(P,H) =12.5 and 8.4 Hz, 3H; CH3P), 2.46 3.16 (m, 8H;
CH2), 3.52 ppm (m, 4H; CH); 13C{1H} NMR (C6D6): d=4.8 (s; CH3Si),
General procedure for the synthesis of phosphino(diazomethane) 2, 6,
13, and 16: One equivalent of the lithium salt of trimethylsilyldiazome-
thane [Me3SiCN2H (5 mmol)
+ BuLi (5 mmol) in THF (10 mL) at
À788C for 30 min] was added dropwise at À788C to a solution of chloro-
phosphine (5 mmol) in THF (10 mL). The reaction mixture was warmed
to room temperature, and stirred for 1 h. The solvent was removed under
vacuum, and the red residue was extracted with pentane (2î5 mL).
After evaporation of pentane, the diazo compounds were obtained as
yellow oils in good yields.
16.3(dd,
J
(P,C) =69.8 and 28.5 Hz; CH3P), 20.3(d, 3J(P,C) =6.4 Hz; CH3C),
20.9 (d, 3J(P,C) =2.8 Hz; CH3C), 21.0 (d, 3J(P,C) =5.5 Hz; CH3C), 22.9 (d,
2
3J(P,C) =7.4 Hz; CH3C), 36.6 (d, 2J(P,C) =8.3Hz; CH 2), 42.4 (d, J(P,C)
=
2
9.2 Hz; CH), 44.4 (s; CH2), 47.9 ppm (d, J(P,C) =28.5 Hz; CH).
2: Yield 95%; IR (toluene): n˜ =2019 cmÀ1 (CN2); 31P{1H} NMR (CDCl3):
Synthesis of keteneimine 11: After of irradiation of 6 overnight in the
presence of three equivalents of tBuNC, 31P NMR spectroscopy indicated
the quantitative formation of keteneimine 11, which was obtained as a
yellow oil, after evaporation of pentane. IR (CDCl3): n˜ =1979 cmÀ1 (>
C=C=N-); 31P{1H} NMR (CDCl3): d=104.1 ppm; 1H NMR (C6D6): d=
0.15 (s, 9H; CH3Si), 1.17 (d, 3J(H,H) =6.4 Hz, 12H; CH3CN), 1.26 (s, 9H;
CH3C), 2.99 3.27 ppm (m, 6H; CH2 and CH); 13C{1H} NMR (C6D6): d=
1
3
d=93.4 ppm; H NMR (CDCl3): d=0.19 (s, 9H; CH3Si), 1.16 (d, J(H,H)
=
6.9 Hz, 3H; CH3), 1.18 (d, 3J(H,H) =6.9 Hz, 3H; CH3), 1.21 (d, J(H,H)
=
3
6.9 Hz, 3H; CH3), 1.32 (d, 3J(H,H) =6.9 Hz, 3H; CH3), 1.73 2.51 (m, 8H;
CH2), 2.98 (m, 2H; CHN), 3.43 ppm (sept d, 3J(H,H) =6.9 Hz,3J(P,H)
=
13.8 Hz, 2H; CHN).
6: Yield 92%; IR (toluene): n˜ =2026 cmÀ1 (CN2); 31P{1H} NMR (CDCl3):
d=106.0 ppm; 1H NMR (CDCl3): d=0.28 (s, 9H; CH3Si), 1.32 (d,
3J(H,H) =6.3Hz, 12H; CH 3C), 3.11 (m, 2H; CH), 3.40 ppm (m, 4H; CH2);
13C{1H} NMR (CDCl3): d=À0.6 (s; CH3Si), 21.9 (d, 3J(P,C) =8.3Hz;
CH3C), 46.8 (d, 2J(P,C) =8.3Hz; CH 2), 48.4 ppm (d, 2J(P,C) =17.5 Hz; CH).
13: Yield 90%; IR (pentane): n˜ =2020 cmÀ1 (CN2); 31P{1H} NMR
(CDCl3): d=97.0 ppm; 1H NMR (CDCl3): d=0.00 (s, 9H; CH3Si), 1.10
(s, 18H; CH3C), 2.79 (m, 2H; CH2), 3.21 ppm (m, 2H; CH2); 13C{1H}
NMR (CDCl3): d=0.7 (d, J(P,C) =3.0 Hz; CH3Si), 29.1 (d, J(P,C) =10.0 Hz;
CH3C), 39.2 (d, 1J(P,C) =15.0 Hz; CN2), 41.1 (d, 2J(P,C) =7.5 Hz; CH3C),
45.3ppm (d, 2J(P,C) =7.5 Hz; CH2).
16: Yield 89%; (S,S)-16 [a]D20 =À18.8, (R,R)-16 [a]2D0 =+18.7 (c=0.06 in
toluene); IR (toluene): n˜ =2018 cmÀ1 (CN2); 31P{1H} NMR (C6D6): d=
116.3ppm; 1H NMR (C6D6): d=0.29 (s, 9H; CH3Si), 1.20, 1.24 (s, 18H;
CH3C), 4.57 (d, 3J(H,H) =8.0 Hz, 1H; CHNP), 4.91 (dd, 3J(H,H) =8.0 Hz,
3J(P,H) =3.0 Hz, 1H; CHNP), 7.21 ppm (m, 10H; Haro); 13C{1H} NMR
(CDCl3): d=1.4 (s; CH3Si), 30.3 (d, 3J(P,C) =11.9 Hz; CCH3), 31.0 (d,
0.5 (s; CH3Si), 22.4 (d, 3J(P,C) =11.0 Hz; CH3CN), 23.1 (d, 3J(P,C) =10.1 Hz;
2
CH3CN), 30.5 (s; CH3C), 47.6 (d, 2J(P,C) =9.2 Hz; CH2), 49.2 (d, J(P,C)
=
2
19.3Hz; CH), 44.4 (s; CH 2), 47.9 ppm (d, J(P,C) =28.5 Hz; CH).
Preparation of phosphino(silyl)carbenes 14 and 17: After irradiation of
13 or 16 overnight at À408C, 31P NMR spectroscopy indicated the quanti-
tative formation of the corresponding carbenes 14 (d=À36.0 ppm) and
17 (d=À32.7 ppm), which are stable at room temperature, and were
used without any further purification.
3
3
Synthesis of cyclopropanes 19: Methyl acrylate (0.6 mmol; 2 equiv) was
added at room temperature to a solution of carbene 17 (0.3mmol) in tol-
uene (3mL). The resulting mixture was stirred at room temperature for
30 min. 31P NMR spectroscopy indicated the quantitative formation of cy-
clopropane 18 (d=126.0 ppm). Treatment of this solution with an excess
of elemental sulfur gave the corresponding thioxophosphoranyl deriva-
tive 19, which was purified by column chromatography (heptane/toluene:
1/1) and recrystallized from a pentane/diethyl ether (50/50) solution as
1985
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¹ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

A. Baceiredo, M. Mikolajczyk, G. Bertrand et al.
FULL PAPER
colorless crystals. m.p. 179 1808C; (S,S,R,R)-19 [a]2D0 =19.1; 80% yield.
(R,R,S,S)-19 [a]2D0 =À19.2 (c=0.05 in CH2Cl2); 85% yield. 31P{1H} NMR
[2] a) H.-U. Reissig, Top. Curr. Chem. 1988, 144, 73; H. N. C. Wong, M.-
Y. Hon, C.-W. Tse, Y.-C. Yip, J. Tanko, T. Hudlicky, Chem. Rev.
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K. Ebel, S. Brode, Angew. Chem. 1995, 107, 1119; Angew. Chem.
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1
(C6D6): d=87.6 ppm; H NMR (C6D6): d=0.30 (s, 9H; CH3Si), 1.24, 1.37
(s, 18H; CH3C), 1.72 (ddd, J=4.0, 5.8 and 11.7 Hz, 1H; CHring), 2.29
(ddd, J=5.8, 6.4 and 13.7 Hz, 1H; CHring), 2.71 (ddd, J=4.0, 6.4 and
23.1 Hz, 1H; CHring), 4.23(dd,
3J(H,H) =8.0 Hz, 3J(P,H) =3.6 Hz 1H;
CHNP), 4.53(d, 3J(H,H) =8.0 Hz, 1H; CHNP), 6.63 7.99 ppm (m, 10H;
Haro); elemental analysis calcd (%) for C30H45N2O2SiPS: C 64.71, H 8.15,
N 5.03; found: C 64.70, H 8.17, N 5.10 for (S,S,R,R)-19, and C 64.75, H
8.20, N 4.98 for (R,R,S,S)-19.
[4] a) D. Enders, H. Gielen, J. Organomet. Chem. 2001, 617, 70; b) L.
Jafarpour, S. P. Nolan, Adv. Organomet. Chem. 2001, 46, 181;
c) W. A. Herrmann, Angew. Chem. 2002, 114, 1342; Angew. Chem.
Int. Ed. 2002, 41, 1290; d) D. Bourissou, O. Guerret, F. P. GabbaÔ, G.
Bertrand, Chem. Rev. 2000, 100, 3 9.
[5] a) A. Igau, A. Baceiredo, G. Trinquier, G. Bertrand, Angew. Chem.
1989, 101, 617; Angew. Chem. Int. Ed. Engl. 1989, 28, 621; b) S.
Goumri-Magnet, T. Kato, H. Gornitzka, A. Baceiredo, G. Bertrand,
J. Am. Chem. Soc. 2000, 122, 4464; c) J. Krysiak, T. Kato, H. Gor-
nitzka, A. Baceiredo, M. Mikolajczyk, G. Bertrand, J. Org. Chem.
2001, 66, 8240.
Crystallographic data for 4, 8, (S,S,R,R)-19 and (R,R,S,S)-19: Data for
all structures were collected at low temperature (T=173(2) K for 4 and
T=193(2) K for the other structures) using an oil-coated shock-cooled
crystal on a Bruker-AXS CCD 1000 diffractometer with MoKa radiation
(l=0.71073ä). The structures were solved by direct methods (SHELXS-
97)[13] and all non-hydrogen atoms were refined anisotropically using the
least-squares method on F2.[14] Crystal data for 4: C16H33N2PSi, Mr =
≈
312.50, triclinic, space group P1 with a=10.366(2), b=10.462(2), c=
10.968(2) ä, a=65.165(3), b=65.088(3), g=67.073(3)8, V=945.7(3) ä3,
Z=2. A total of 5492 reflections (3779 independent, Rint =0.0830) were
collected, largest residual electron density: 0.697 eäÀ3, R1=0.0519 (for
I>2s(I)) and wR2=0.1448 (all data). Crystal data for 8: C24H54N6P2Si2,
Mr =544.85, monoclinic, space group P21/c with a=18.318(2), b=
[6] T. Kato, H. Gornitzka, A. Baceiredo, A. Savin, G. Bertrand, J. Am.
Chem. Soc. 2000, 122, 998.
11.540(2), c=16.753(2) ä, b=116.009(2)8, V=3182.7(7) ä3, Z=4.
A
[7] a) The trans-1,2-diaminocyclohexane motif was selected because it is
a very effective chiral building block and is readily accessible (Al-
drich): J. F. K. M¸ller, M. Zehnder, F. Barbosa, B. Spingler, Helv.
Chim. Acta 1999, 82, 1486; b) S. E. Denmark, H. Stadler, R. L.
Dorow, J. H. Kim, J. Org. Chem. 1991, 56, 5063; c) P. Mangeney, T.
Tejero, A. Alexakis, F. Grosjean, J. F. Normant, Synthesis 1988, 255.
[8] A few examples of 1,3-diphosphetes have been reported: a) B. Neu-
m¸ller, E. Fluck, Phosphorus Sulfur Relat. Elem. 1986, 29, 23 ;
b) H. H. Karsch, T. Rupprich, M. Heckel, Chem. Ber. 1995, 128,
959c) H. Keller, G. Maas, M. Regitz, Tetrahedron Lett. 1986, 27,
1903.
total of 15136 reflections (5189 independent, Rint =0.0587) were collect-
ed, largest residual electron density: 0.647 eäÀ3, R1=0.0528 (for I>
2s(I)) and wR2=0.1505 (all data). Crystal data for (S,S,R,R)-19:
C30H45N2O2PSSi, Mr =556.80, orthorhombic, space group P212121 with
a=10.5171(6), b=15.4110(8), c=19.2820(10) ä, V=3125.2(3) ä3, Z=4.
A total of 18390 reflections (6398 independent, Rint =0.0316) were col-
lected, largest residual electron density: 0.254 eäÀ3, R1=0.0305 (for I>
2s(I)) and wR2=0.0742 (all data). Crystal data for (R,R,S,S)-19:
C30H45N2O2PSSi, Mr =556.80, orthorhombic, space group P212121 with
a=10.528(1), b=15.439(2), c=19.311(2) ä, V=3138.8(6) ä3, Z=4. A
[9] S. Goumri-Magnet, O. Polishchuk, H. Gornitzka, C. J. Marsden, A.
Baceiredo, G. Bertrand, 1999, 111, 3 93 8A; ngew. Chem. Int. Ed.
1999, 38, 3727.
total of 23078 reflections (6391 independent,
Rint =0.0355) were collect-
ed, largest residual electron density residue: 0.230 eäÀ3, R1=0.0332 (for
I>2s(I)) and wR2=0.0761 (all data).
[10] H. Staudinger, J. Meyer, Helv. Chim. Acta 1919, 2, 635.
[11] Phosphoranyl oxiranes were obtained in a highly stereoselective
manner by reaction of phosphanyl(silyl)carbenes with aldehydes:
a) O. Illa, H. Gornitzka, V. Branchadell, A. Baceiredo, G. Bertrand,
R. M. OrtuÊo, Eur. J. Org. Chem. 2003, 3147; b) O. Illa, H. Gornitz-
ka, A. Baceiredo, G. Bertrand, V. Branchadell, R. M. OrtuÊo, J.
Org. Chem. 2003, 68, 7707.
CCDC-224336 (4), CCDC-224337 (8), CCDC-224338 ((S,S,R,R)-19), and
CCDC-224339 ((R,R,S,S)-19) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crys-
tallographic data Centre, 12 Union Road, Cambridge, CB21EZ, UK; fax:
(+44)1223-336-033 or e-mail: deposit@ccdc.cam.ac.uk).
[12] a) V. Blazis, A. de la Cruz, K. Koeller, C. D. Spilling, Phosphorus,
Phosphorus Sulfur Silicon Relat. Elem. 1993, 75, 159; b) C. Stader,
Dissertation, Universit‰t Bayreuth, 1988; c) R. B. King, P. M. Sun-
daram, J. Org. Chem. 1984, 49, 1784.
Acknowledgment
[13] G. M. Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467
[14] G. M. Sheldrick, SHELXL-97, Program for Crystal Structure Re-
finement, University of Gˆttingen, Germany, 1997.
Thanks are due to the CNRS for financial support of this work, and to
the French Polish Associate European Laboratory for a grant to J. K.
[1] a) Small Ring Compounds in Organic Synthesis VI, Vol. 207 (Ed.: A.
de Meijere), Springer, Berlin, 2000; b) Methods of Organic Chemis-
try (Houben-Weyl), Vol. E 17 (Eds.: A. de Meijere, A. Schaumann),
Thieme, Stuttgart, 1997.
Received: November 14, 2003
Revised: January 7, 2004 [F5722]
1986
¹ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
Chem. Eur. J. 2004, 10, 1982 1986