Synthesis of phosphanyl sulfoximines through phospha-michael reaction of alkenyl sulfoximines and their evaluation as chiral bidentate 1, 5-N, P ligands for palladium in asymmetric allylic alkylation

Article abstract of DOI:10.1002/ejoc.200901462

The intermolecular phospha-Michael reaction of cyclic and acyclic alkenyl sulfoximines proceeds readily and yields the corresponding phosphanyl sulfoximines in good yield. The asymmetric induction provided, by sulfoximine group in C-P bond formation is ap

Full text of DOI:10.1002/ejoc.200901462

FULL PAPER
DOI: 10.1002/ejoc.200901462
Synthesis of Phosphanyl Sulfoximines Through Phospha-Michael Reaction of
Alkenyl Sulfoximines and Their Evaluation as Chiral Bidentate 1,5-N,P
Ligands for Palladium in Asymmetric Allylic Alkylation
Fabien Lemasson,[a][‡] Hans-Joachim Gais,*[a] Jan Runsink,[a] and Gerhard Raabe[a]
Keywords: Palladium / Alkylation / Asymmetric allylic alkylation / Sulfoximine / Phospha-Michael reaction
The intermolecular phospha-Michael reaction of cyclic and
acyclic alkenyl sulfoximines proceeds readily and yields the
corresponding phosphanyl sulfoximines in good yield. The
asymmetric induction provided by sulfoximine group in C–P
bond formation is apparently only low. The configuration of
three phosphanyl sulfoximine–boranes has been determined
by X-ray crystal structure analysis. The ability of the phos-
phanyl sulfoximines to act as ligand in Pd-catalyzed asym-
metric allylic alkylation was studied with pairs of dia-
stereomeric cyclic and acyclic derivatives carrying different
substituents at the N atom. This study showed that the sub-
stituent at the N atom and both the chirality of the backbone
and sulfoximine group play a crucial role in determining the
enantioselectivity of the allylic alkylation. The Pd-catalyzed
reaction of the racemic 1,3-diphenylallyl acetate with the mal-
onate anion in the presence of a cyclic N-benzyl-substituted
phosphanyl sulfoximine gives the corresponding malonate
with 97% ee in 98% yield. The similar alkylation with di-
alkyl-substituted allylic acetates proceeds only with medium
enantioselectivity. The bidentate 1,5-N,P-coordination of the
Pd atom by the phosphanyl sulfoximine was confirmed by
NMR experiments of a π-1,3-diphenylallyl-PdII complex con-
taining a cyclohexyl phosphanyl sulfoximine as ligand. The
cyclohexane ring of the free cyclic phosphanyl sulfoximines
adopts in solution and in the crystal a conformation in which
the sulfoximine and phosphanyl group are both in a pseudo
axial position. The coordination of the ligand to the Pd atom
causes an inversion of the cyclohexane ring, which places
the two groups in equatorial position.
ral backbone, could serve as bidentate 1,5-N,P ligands for
transition metals. The 1,4-N,P ligands I and II probably
form chelates of type III and IV, respectively, which are ex-
pected to possess a relatively low S–N rotational barri-
er.[8b,8c] This provides conformational flexibility for the
S(O)Ar(R) group being placed in close proximity to the
metal atom. In contrast, the phosphanyl sulfoximines V and
VI are in principle capable to give chelates of type VII and
VIII, respectively, the S atom of which is part of the six-
membered ring. Incorporation of the chiral sulfoximine
group into the ring of VII and VIII could perhaps allow an
efficient transmission of the effects exerted by the substitu-
ents of the backbone via the N- and P atom across the
metal atom to its organic residues. In this context the nature
of the group R1, which is in close proximity to the metal
atom, could be of special importance. While its steric size
might be significant in the transmission of the substituent
effects, its electronic nature will affect the Lewis basicity of
the sulfoximine group.[1] Formation of N,P chelates of type
VII and VIII and not O,P chelates should be preferred be-
cause of the higher propensity of the N atom of sulfox-
imines to bind Lewis and Brønsted acids.[1,8b] The variation
of the substituents R1, R2 and R3 of V and ring size of VI
could provide a synthetic means to perhaps influence the
performance of the ligand.[9] A large number of bidentate
N,P ligands have been synthesized and successfully applied
Introduction
The sulfonimidoyl group has gained a firm place as chi-
ral auxiliary in asymmetric synthesis.[1,2] Its versatility stems
from an almost unique combination of features including
configurational stability, carbanion stabilization, nucleofu-
gacity, nucleophilicity, Brønsted and Lewis basicity, and ac-
tivation in ortho-lithiation. In recent years sulfoximines have
found interest as chiral ligands in asymmetric transition
metal catalysis.[3] Amongst the various sulfoximines which
have been designed for transition metals[4] the aryl phos-
phanyl sulfoximine I[5] and alkyl phosphanyl sulfoximine
II[6] (Figure 1)[7,8] showed considerable promise as 1,4-N,P
ligands in Ir-catalyzed asymmetric hydrogenation[4n,4o,5]
and Pd-catalyzed allylic alkylation.[5,6] We envisioned the
synthesis and study of acyclic and cyclic phosphanyl sulf-
oximines of type V and VI, respectively, as potential ligands
for transition metals. Phosphanyl sulfoximines V and VI,
which have besides the chiral sulfoximine group also a chi-
[a] Institute of Organic Chemistry, RWTH Aachen University,
Landoltweg 1, 52056 Aachen, Germany
Fax: +49-241-8092665
E-mail: Gais@RWTH-Aachen.de
[‡] New address: Institute of Nanotechnology, Karlsruhe Institute
of Technology,
Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopolds-
hafen, Germany
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F. Lemasson, H.-J. Gais, J. Runsink, G. Raabe
FULL PAPER
in asymmetric transition metal catalysis[9] and particularly N atom followed by an addition/elimination sequence
in Pd-catalyzed allylic alkylation[10b,10d,11] However, N,P li- (Scheme 1, Table 1). Sulfoximine 1 in turn is readily avail-
gands of type V and VI carrying three consecutive able in enantiomerically pure form through an efficient
stereogenic centers in the single bond[7] composed back- resolution with 10-camphorsulfonic acid following the
bone connecting the N- and P atom are rare.[12] Previously, method of half-quantity.[19]
we had studied the potential of the Pd-catalyzed allylic alk-
ylation in asymmetric C–S and C–O bond formation and
kinetic resolution.[13] Therefore, we were primarily inter-
ested in the evaluation of phosphanyl sulfoximines of type
V and VI as N,P ligands for the Pd atom. We envisioned a
synthesis of phosphanyl sulfoximines V and VI through a
phospha-Michael reaction (PMR) of the corresponding
Scheme 1. Synthesis of the alkenyl sulfoximines 6–9 starting from
sulfoximine 1.
alkenyl sulfoximines with an alkali phosphide. While mainly
intramolecular MRs of alkenyl sulfoximines with O-,[14]
N-,[15] S-[16] and C-nucleophiles[17] are well documented,
only one example of a intermolecular PMR of a vinyl sulf-
oximine had been described.[6] Therefore, the evaluation of
the potential of the PMR for the synthesis of phosphanyl
sulfoximines was of interest. In this paper we describe the
synthesis of phosphanyl sulfoximines of type V and VI
through PMR of alkenyl sulfoximines and their evaluation
as ligands in Pd0-catalyzed allylic alkylation[18] together
with a NMR spectroscopic determination of the mode of
their coordination to the Pd atom.
Table 1. Synthesis of the N-substituted S-methyl sulfoximines (MS)
2–5 and alkenyl sulfoximines (AS) 6–9.
R1
MS Conditions
Yield (%) AS Yield (%)
Me
2
3
HCHO, HCO2H,
H2SO4, reflux, 3 d
PhCH2Br,
93
90
6[a]
88
91
CH2Ph
7[a]
KH, Bu4NBr,
DME, room temp., 1 h
TolSO2Cl,
pyridine, room temp., 12 h
tBuPh2SiCl,
SO2Tol
4
5
92
96
8[a]
9[a]
92
85
SitBuPh2
ImH, DMF,
0 °C to room temp., 7 h
[a] 1. nBuLi, THF, –78 °C; 2. PhCHO, –78 °C; 3. ClCO2Me, –78 °C
to room temp.; 4. DBU, –78 °C to room temp.
While the N-methyl sulfoximine 2 was prepared in 93%
yield through Eschweiler–Clark methylation of 1,[20] its benz-
ylation using a slightly modification of the literature proto-
col afforded the N-benzyl sulfoximine 3[21] in 90% yield.
Tosylation of sulfoximine 1 with tosyl chloride in pyridine
furnished the N-tolylsulfonyl sulfoximine 4[22] in 92% yield,
and silylation of 1 with tBuPh2SiCl and imidazole in di-
methylformamide (DMF) gave the N-silyl sulfoximine 5[23]
in 96% yield. The addition/elimination route[24,25] was se-
lected of the various methods available for the synthesis of
alkenyl sulfoximines,[1] because of its simplicity and high
yield. The one pot procedure involved the lithiation of the
S-methyl sulfoximines 2–5 with nBuLi and the treatment of
the corresponding carbanions with benzaldehyde, which
gave the corresponding alkoxides as mixtures of epi-
mers.[23,26] The alkoxides were not isolated but treated with
ClCO2Me, which afforded the corresponding carbonates.
Treatment of the carbonates without prior isolation with
1.8-diazabicyclo[5.4.0]undec-7-ene (DBU) furnished the
corresponding alkenyl sulfoximines 6–9 as E-isomers in 85–
92% yield.[27,28]
Figure 1. 1,4- and 1,5-N,P-Phosphanyl sulfoximines and their metal
chelates.
Results and Discussion
Acyclic Alkenyl Sulfoximines
The substituent R1 at the N atom of V and VI was ex-
pected to be of importance for the performance of the phos-
phanyl sulfoximines as ligands for the Pd atom. The ability
of sulfoximines V and VI to function as a 1,5-N,P chelate
ligand will strongly depend on the Lewis basicity of the N
atom. While alkyl groups at the N atom enhance the Lewis
basicity of the sulfoximine group, electron-withdrawing
substituents have the opposite effect.[1] Steric effects exerted
by the substituent at the N atom of V and VI could also
influence their coordinating ability. Based on these consid-
erations the methyl, benzyl, p-tolysulfonyl and tert-butyldi-
phenylsilyl group were selected as substituents at the N
Cycloalkenyl Sulfoximines
A synthesis of cycloalkenyl sulfoximines of type IX (Fig-
atom of the phosphanyl sulfoximines. The acyclic alkenyl ure 2) was not available at the beginning of our investiga-
sulfoximines 6–9 were prepared starting from the NH-sulf- tion. Two approaches to sulfoximines IX were envisioned.
oximine 1 in two steps including a functionalization at the Route A features the construction of the carbocycle of IX
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Asymmetric Allylic Alkylation
through a cycloalkylation of the S-methyl sulfoximine XII
with dihalide XIII to yield sulfoximine XI.[29] Halogenation
of XI with formation of halide X[30] and its subsequent eli-
mination could afford the alkenyl sulfoximine IX. While the
α-halogenation of sulfoximines had been described, nothing
was known, however, about the feasibility of an elimination
of α-halo sulfoximines with formation of the corresponding
alkenyl sulfoximines. Route B encompasses the synthesis of
the ω-chloro(bromo)alkenyl sulfoximine XV by the ad-
dition/elimination route from sulfoximine XII and the ω-
halo aldehyde XVI. Lithiation of XV and cyclization of the
α-lithioalkenyl sulfoximine XIV could afford IX.[31] Follow-
ing route A, cycloalkylation of sulfoximine 2 upon the suc-
cessive reaction with 1.2 equiv. of nBuLi and 1.2 equiv. of
1,5-dibromopentane gave the cyclohexyl sulfoximine 10 in
50% yield together with 50% of the starting sulfoximine 2
(Scheme 2).[29,30] The successive treatment of sulfoximine 10
with 1.2 equiv. of nBuLi and 2 equiv. of 1,2-dibromo-
1,1,2,2-tetrachloroethane afforded an inseparable 55:45
mixture of the α-chloro and α-bromo sulfoximines 11 and
12, respectively, in 91% total yield. The mixture of 11 and
12 was then subjected to a treatment with tBuOK in THF.
Unfortunately, this gave only traces of the desired alkenyl
sulfoximine. Instead, sulfinamide 13 and the cyclohexyl
sulfoximine 10 were isolated as the major products. Forma-
tion of the sulfinamide and the cyclohexyl sulfoximine can
be ascribed to an elimination of 11 and 12 with formation
of 1-chloro(bromo)cyclohexene (not isolated) and a halo-
philic reaction,[32] respectively.
Scheme 2. Attempted synthesis of a cycloalkenyl sulfoximine
through α-halogenation and elimination.
enyl sulfoximines 15 and 16 with 1 equiv. of LDA[33] fur-
nished the corresponding cycloalkenyl sulfoximines 17 and
18 in 80% and 92% yield, respectively.
Scheme 3. Synthesis of the cycloalkenyl sulfoximines through α-
lithiation and cyclization of the 6-bromoalkenyl sulfoximines.
PMR of Alkenyl Sulfoximines
Having the desired alkenyl and cycloalkenyl sulfoximines
in hand, their PMR was investigated. The treatment of the
alkenyl sulfoximine 6 with 1.1 equiv. of KPPh2 at –78 °C in
THF and the subsequent successive addition of 2 equiv. of
MeOH, 2.2 equiv. of BH3·THF and HCl (method A) gave
the phosphane–borane 19 as a single diastereomer in but
only 18% yield (Scheme 4, Table 2, entry 1). Better yields
were obtained by using HPPh2 and 10 mol-% of tBuOK
(method B). The alkenyl sulfoximine 6 furnished under
these conditions a mixture of the diastereomeric phos-
phane–boranes 19 and 20 in a ratio of 78:22 in 78% yield
(entry 2). The alkenyl sulfoximines 7–9 afforded under the
same conditions the corresponding phosphane–boranes 21–
26 in good yields as mixtures of diastereomers (entries 3–
5). The diastereomeric phosphane–boranes were separated
by crystallization and/or chromatography. The absolute
configuration of phosphane–boranes ent-20[34] and 25 was
determined by X-ray crystal structure analysis (see below).
Characteristic shift differences of the signals of the Ph
1
group at the stereogenic C atom were observed in the H
Figure 2. Retrosynthesis of the cycloalkenyl sulfoximines.
Following the alternative route B, sulfoximines 2 and 3
were successively treated with nBuLi, 5-bromopentanal,
ClCO2Me and DBU, which afforded the corresponding 6-
bromoalkenyl sulfoximines 15 and 16 in 83% and 77%
yield, respectively (Scheme 3). Reaction of the 6-bromoalk- Scheme 4. PMR of the alkenyl sulfoximines 6–9.
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F. Lemasson, H.-J. Gais, J. Runsink, G. Raabe
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NMR spectra of the SSRC- and SSSC-configured phos-
The sulfonimidoyl group of the alkenyl sulfoximines ap-
phane–boranes, which allowed a configurational assign- parently exerts, irrespective of its N-substituent, only a low
ment of 19–24.
degree of asymmetric induction in the addition of MPPh2
to the double bond. However, it cannot be excluded that
C–P bond formation was reversible under the conditions
applied and the PMR was thus under thermodynamic con-
trol. While the nearly unselective formation of the phos-
phanyl sulfoximines was unsatisfying in synthetic terms, it
provided a most welcome tool to study the influence of the
configuration of the sterogenic centers upon the asymmetric
induction in allylic alkylation (see below).
The highly selective formation of the trans-configured cy-
clic phosphanyl sulfoximines 35–38 in the reaction of the
corresponding cycloalkenyl sulfoximines with HPPh2 ac-
cording to method B can be rationalized as follows. The
addition of KPPh2 to the double bond of 17 and 18 is unse-
lective giving the potassium α-sulfonimidoyl carbanion salts
31 and 33 and their diastereomers 32 and 34, respectively
(Scheme 6). Based on the current knowledge of the struc-
ture of α-sulfonimidoyl carbanion salts,[35] the potassium
salts are expected to adopt a structure which is charac-
terized by (1) a pyramidalized anionic C atom, (2) the lack
of a C–K bond and (3) a six-membered ring, in which the
K atom is coordinated by the P and N atom. Because of
steric effects, the bicyclic ring system with the bridgehead
anionic C atom adopts the trans-configuration. Protonation
of carbanions 31–34 should occur preferentially from the
direction of the pyramidalization giving the corresponding
trans-configured phosphanyl sulfoximines 35–38.
Table 2. PMR of the alkenyl sulfoximines 6–9 and cycloalkenyl sul-
foximines 17 and 18.
Entry Starting R1
material
Method[a] Phosphanyl
sulfoximine
dr[b]
Yield
(%)
1
2
3
4
5
6
7
8
6
6
7
8
9
17
18
18
Me
Me
A
B
B
B
B
B
B
C
19, 20
19, 20
21, 22
23, 24
25, 26
27, 28
29, 30
29, 30
Ն 98:2
78:22
64:36
27:73
58:42
50:50
50:50
25:75
18, 0
61, 17
53, 25
18, 51
40, 32
35, 46
CH2Ph
SO2Tol
SitBuPh2
Me
CH2Ph
CH2Ph
41, 39
[c]
[a] A: i. 1.1 equiv. KPPh2, –78 °C, 30 min. ii. 2 equiv. MeOH,
–78 °C, 2 h. iii BH3·THF, 0 °C, 2 h. iv. 1  HCl until pH 5 was
reached. B: 1.1 equiv. HPPh2, 0.1 equiv. tBuOK, room temp., 1–
2 h. ii. 2.2 equiv. BH3·THF, 0 °C, 1 h. iii. 1  HCl until pH 5. C:
2 equiv. HPPh2, 1.9 equiv. nBuLi, –78 °C, 1 h. ii. 1.9 equiv. (Ϯ)-10-
camphorsulfonic acid, –78 °C. iii. 2.2 equiv. BH3·THF, 0 °C. iv. 1 
HCl until pH 5 was reached. [b] The ratio SSRC/SSSC and SSRCRC/
SSSCSC was determined by chiral HPLC (see Exp. Sect.) or 1H
NMR spectroscopy. [c] Not determined.
Gratifyingly, the cycloalkenyl sulfoximine 17 also under-
went a PMR upon the treatment with HPPh2 and tBuOK
(Scheme 5, entry 6) and gave the two trans-configured dia-
stereomeric phosphane–boranes 27 and 28 in a ratio of
50:50 (1H NMR) in 35% and 46% yield, respectively, after
separation by chromatography. The similar PMR of the
benzyl-substituted cycloalkenyl sulfoximine 18 with HPPh2
according to method B afforded a 50:50 mixture of the dia-
stereomeric phosphane–boranes 29 and 30 (entry 7). Sepa-
ration by chromatography gave 29 and 30 in 41% and 39%
yield, respectively. The reaction of 18 with LiPPh2 at low
temperature according to method C, which included the use
of 2 equiv. of HPPh2 and 1.9 equiv. of nBuLi, furnished the
phosphane–boranes 29 and 30 in a ratio of 25:75 (entry 8).
In no experiment with 17 and 18 was the formation of the
other two possible diastereomers observed. The absolute
configuration of the SSRCRC-configured phosphane–
borane 29 was determined by X-ray crystal structure analy-
sis (see below). The configuration of the phosphane–bo-
1
ranes 21–24 was assigned based on characteristic H NMR
shift differences between the SSRCRC- and SSSCSC-config-
ured diastereomers (see below).
Scheme 6. Stereochemical course of the PMR of the cycloalkenyl
sulfoximines 17 and 18 (coordination of the K atom by THF not
shown).
X-ray Crystal Structure Analysis of Phosphanyl
Sulfoximine–Boranes
The absolute configuration of the phosphane–boranes
ent-20, 25 and 29 was determined by X-ray crystal structure
Scheme 5. PMR of the cycloalkenyl sulfoximines 17 and 18.
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Asymmetric Allylic Alkylation
analysis.[36] The acyclic phosphanyl N-methyl sulfoximine– points towards the cyclohexane ring and the larger phenyl-
borane 20 (Figure 3) and phosphanyl N-silyl sulfoximine– and N-benzyl group are orientated in the opposite direc-
borane 25 (Figure 4) adopt in the crystal almost an anti tion.
conformation at the Ca–Cb bond as revealed by S–Ca–Cb–
P dihedral angles of 165.4° and 145.7°, respectively. In the
crystal, the six-membered ring of the cyclic phosphanyl N- NMR Spectroscopy of Cyclic Phosphane–Boranes
benzyl sulfoximine–borane 29 has a distorted chair-like
It was of interest to see whether the cyclohexane ring of
conformation, in which the sulfoximine and the phosphanyl
the cyclic phosphane–boranes 27–30 adopts in solution a
group adopt a pseudo axial position (Figure 5). The S–Ca–
similar conformation as the one of the phosphane–borane
Cb–P and Ha–Ca–Cb–Hb dihedral angles are 140.7° and
29 in the crystal. A bidentate coordination of the Pd atom
82°, respectively. The sulfoximine group of 29 adopts a Ca-
by the phosphanyl sulfoximines 35–38 would require an in-
S conformation in the crystal, in which the smaller O atom
version of the chair-like conformation of the cyclohexane
ring, bringing the phosphanyl and sulfoximine group in a
pseudo equatorial position. Thus, NMR spectroscopy of
the free ligands 35–38 and their Pd0 or PdII allyl complexes
could provide a means to prove a 1,5-N,P chelation of the
1
Pd atom. The H NMR spectra of 27–30 showed no mea-
surable coupling between Ha and Hb and the COESY spec-
tra revealed the absence of a correlation peak between both
H atoms. A NOE was observed between Ha and Hb of the
phosphane–boranes 27 and 28 (29 and 30 were not investi-
gated). Both signals of Ha and Hb of the phosphane–
boranes 27–30 appeared as a doublet of doublet and both
showed a coupling with the P atom and the neighboring
protons Hfax and Hcax, respectively. The couplings 3J(Ha,H-
Figure 3. Structure of the acyclic phosphanyl N-methyl sulfox-
imine–borane ent-20 in the crystal. Selected bond lengths: S–O
1.455(2), S–N 1.521(4), C–S 1.797(4), P–B 1.923(3), C–P 1.853(5).
3
feq) and J(Hb,Hceq) were not observed, which are therefore
smaller than 2 Hz. The J values of 27 and 28 are shown in
Figure 6. These results are in accordance with a dihedral
angle between Ha and Hb of approximately 80°. Thus, the
phosphanyl sulfoximines 27–30 adopt in solution a similar
conformation as 29 in the crystal, in which both the sulfox-
imine and phosphanyl group are in a pseudo axial position
and the S–Ca–Cb–P dihydral angle is approximately 140°.
Figure 4. Structure of the acyclic phosphanyl N-silyl sulfoximine–
borane 25 in the crystal. Selected bond lengths: S–O 1.453(4), S–
N 1.489(4), C–S 1.796(5), P–B 1.913(5), C–P 1.858(4).
Figure 6. Coupling constants of the cyclic phosphane–boranes 27
and 28.
1
A major difference was observed between the H NMR
spectra of the SSRCRC-configured phosphane–boranes 27
and 29 and those of the corresponding SSSCSC-configured
phosphane–boranes 28 and 30. In the case of the SSRCRC-
configured phosphane–boranes 27 and 29, the signal of Hb
appeared at δ = 4.57 ppm and 4.70 ppm, respectively, which
is close to the average value found for the acyclic phos-
Figure 5. Structure of the cyclic phosphanyl N-benzyl sulfoximine–
borane 29 in the crystal. Selected bond lengths: S–O 1.434(4), S–
N 1.492(4), C–S 1.830(5), P–B 1.927(6), C–P 1.841(4).
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F. Lemasson, H.-J. Gais, J. Runsink, G. Raabe
FULL PAPER
phane–boranes (δ =4.5 ppm). In contrast, the signal of Hb 27–30 with 1.05 equiv. of 1,4-diazabicyclo[2.2.2]octane
of the SSSCSC-configured phosphane–boranes 28 and 30 (DABCO) in dry degassed toluene at 40 °C (Table 3).
appeared at δ = 3.53 ppm and 3.70 ppm, respectively. In
Deboronation of the acyclic phosphane–boranes 19–26
addition, the signal of Hfeq of the SSRCRC-configured sulf- was slower (2 h) than that of the cyclic phosphane–boranes
oximines 27 and 29 experienced a high-field shift of 27–30 (1 h). The progress of the deboronation was moni-
0.73 ppm and 0.79 ppm, respectively, relative to those of 28 tored by 31P NMR spectroscopy. The corresponding phos-
and 30. The high-field displacements of the signal of Hb of phanes 35–45 were isolated in high yield by filtration of
28 and 30 and that of Hfeq of 27 and 29 are most likely due the crude reaction mixture through a plug of silica gel and
to the anisotropic effect of the phenyl group at the S atom. removal of the solvent in vacuo. Phosphanes 35–45 are sen-
Sulfoximines 27–30 adopt a Ca-S conformation in which the sitive towards dioxygen.
smallest substituent, the O atom, points below the cyclohex-
ane ring because of a minimization of steric interaction
(Figure 7 and cf. Figure 5). While the phenyl group of the
SSSCSC-configured sulfoximines 28 and 30 points towards
Hb, that of the SSRCRC-configured sulfoximines 27 and 29
Palladium-Catalyzed Allylic Alkylation with Phosphanyl
Sulfoximines as Ligands
points towards Hfeq
.
The acyclic phosphanyl sulfoximines 39–44 and the cyclic
phosphanyl sulfoximines 35–38 were tested as ligands in the
Pd0-catalyzed asymmetric allylic alkylation of racemic 1,3-
diphenylallyl acetate rac-46 by using 1.5 mol-% of Pd2(dba)3·
CHCl3 and 3 mol-% of the ligand. Acetate rac-46 was se-
lected because of its general use as standard for the evalu-
ation of ligands for the Pd atom.[10,11] The dimethyl malon-
ate anion served as nucleophile, which was generated by
using the combination of dimethyl malonate, bis(trimethyl-
silyl)acetamide (BSA) and a catalytic amount of MOAc.[37]
The Pd0·phosphanyl sulfoximine complexes were prepared
by heating the corresponding phosphanyl sulfoximines and
Pd2(dba)3·CHCl3 at 40 °C for 2 h. In preliminary experi-
ments the SSRC-configured phosphanyl-N-methylsulfoxim-
ine 39 was used as ligand. The variation of the ligand-to-
palladium ratio affected the yield as well as the ee value of
malonate (R)-47 (Scheme 7, Table 4, entries 1–3). At a li-
gand-to-palladium ratio of 1:1 malonate (R)-47 was isolated
in 40% yield with 63% ee (entry 3). While an increase of
the ratio led to a much higher yield of malonate (R)-47, its
ee value dramatically decreased (entry 2). At a ligand-to-
palladium ratio of 0.66:1 malonate (R)-47 was isolated in
only 12% yield but with an ee value of 61% (entry 1). A
full conversion of acetate rac-46 was achieved by using Li+
Figure 7. Ca-S Conformation of the sulfoximine group of the cyclic
phosphane–boranes 27–30.
Deboronation of Phosphane–Boranes
The free acyclic and cyclic phosphanyl sulfoximines 39–
45 and 35–38, respectively, were obtained through treat-
ment of the corresponding phosphane–boranes 19–26 and
Table 3. Deboronation of phosphane–boranes 19–30 with formation
of the corresponding phosphanyl sulfoximines 39–45 and 35–38.
+
instead of K+ as counterion (entry 5). The use of the NBu4
as counterion resulted in a lower enantioselectivity of the
alkylation (entry 4).
Phosphane– Phosphanyl R1
R2
R3 Config. Yield (%)
borane
sulfoximine
19
20
21
22
23
25
26
27
28
29
30
39
40
41
42
43
44
45
35
36
37
38
Me
Me
H
H
H
H
H
H
H
Ph SSRC
Ph SSSC
Ph SSRC
Ph SSSC
Ph SSRC
Ph SSRC
Ph SSSC
96
94
98
94
94
92
93
97
91
97
93
CH2Ph
CH2Ph
SO2Tol
SitBuPh2
SitBuPh2
Me
Me
CH2Ph
CH2Ph
Scheme 7. Pd-catalyzed allylic alkylation of acetate rac-46 with
phosphanyl sulfoximine 39 as ligand.
The pronounced dependency of the enantioselectivity
and yield on the ligand-to-metal ratio can be rationalized
by a mechanistic scheme which was previously proposed in
order to explain similar ligand-to-palladium effects in the
case of a phosphanyl-oxazoline ligand.[38] Accordingly, a
–(CH2)4– SSRCRC
–(CH2)4– SSSCSC
–(CH2)4– SSRCRC
–(CH2)4– SSSCSC
2162
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 2157–2175

Asymmetric Allylic Alkylation
Table 4. Effect of the ligand to Pd0 ratio and cation on the Pd- will have a high and the later two only a low tendency to
catalyzed allylic alkylation of acetate rac-46 with phosphanyl sulf-
act as bidentate ligands for the Pd atom. A screening of
several solvents showed CH2Cl2 to be the best one in terms
of activity of the catalyst (entries 3, 9 and 10).
oximine 39 as ligand.
Entry
39/Pd0[a]
M
47
Yield (%)
ee[b]
Config.[c]
1
2
3
4
5
0.66:1
2.2:1
1:1
1:1
1:1
K
K
K
NBu4
Li
12
96
40
54
96
61
46
63
43
65
R
R
R
R
R
[a] 3 mol-% of Pd0 was used. [b] The ee value of malonate 47 was
determined by chiral HPLC. [c] The absolute configuration of ma-
lonate 47 was determined by comparison of the optical rotation
with the literature value.
Scheme 8. Pd-catalyzed allylic alkylation of acetate rac-46 with acy-
clic phosphanyl sulfoximines as ligand.
Table 5. Pd-catalyzed allylic alkylation of acetate rac-46 under vari-
chelated π-allyl-Pd complex predominates at ligand-to-
metal ratios of 1:1 or 0.66:1, which reacts with the nucleo-
ation of the acyclic phosphanyl sulfoximine.
phile with medium enantioselectivity. At a ligand-to-metal Entry Ligand[a] R1
Config. Solvent
47
Yield (%) ee Config.
ratio of 2.2:1 a second π-allyl-Pd complex with two mole-
cules of 39 coordinated via the P atom to the Pd atom is
formed in considerable amounts, which reacts faster but
with lower enantioselectivity.
1
2
3
39
40
41
42
43
44
41
41
41
41
Me
Me
SSRC
SSSC
SSRC
SSSC
SSRC
SSSC
SSRC
SSRC
SSRC
SSRC
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH3CN
PhCH3
96
40
98
72
17
5
40
57
28
5
65
10
82
40
5
15
89
90
69
88
R
S
R
S
CH2Ph
CH2Ph
SO2Tol
SitBuPh2
CH2Ph
CH2Ph
CH2Ph
CH2Ph
4
Interestingly, application of the diastereomeric SSSC-
configured phosphanyl sulfoximine 40 as ligand gave the
(S)-configured malonate (S)-47 in 40% yield with only 10%
ee (Scheme 8, Table 5, entry 2). This results shows that not
only the stereogenic C atom but also the stereogenic S atom
plays an important role in the enantioselectivity and activity
of the catalyst. The N-substituent has also a significant ef-
fect on the selectivity of the catalyst. While the alkylation in
the presence of the N-methyl-substituted phosphanyl sulf-
oximine 39 gave malonate (R)-47 with 65% ee, that with the
5[b]
6
S
R
R
R
R
R
7[c]
8[d]
9
10
[a] L/Pd ratio 1:1. [b] KOAc was used instead of LiOAc. [c] Carried
out at –1 °C. [d] Carried out at –1 °C using 6 mol-% of Pd and
ligand.
Having recorded promising enantioselectivities with the
N-benzyl-substituted phosphanyl sulfoximine 41 gave (R)- acyclic phosphanyl sulfoximines, it was of interest to test
47 in almost quantitative yield with 82% ee (entries 1 and the cyclic phosphanyl sulfoximines. These phosphanyl sulf-
3). The decrease of the reaction temperature to –1 °C led to oximines should show a higher tendency to form a chelate
a reduced conversion but higher enantioselectivity (entry 7). with the Pd atom provided the cyclohexane ring can un-
An increase of the catalyst loading had only a minor effect dergo the required conformational change (cf. Figure 5).
on the yield of malonate (R)-47 (entry 8). The SSSC-config- Application of the phosphanyl N-methyl sulfoximine 35 in
ured N-benzyl-substituted phosphanyl sulfoximine 42 gave the reaction of rac-46 with the malonate anion, under same
a more active catalyst as compared the SSSC-configured N- conditions as before, gave malonate (R)-47 in almost quan-
methyl ligand 40. Here, malonate (S)-47 was isolated in titative yield with 86% ee (Scheme 9, Table 6, entry 1). The
72% yield with an ee value of 40% (entry 4). Table 5 reveals doubling of the ligand-to-metal ratio had no bearing on the
that there are matched and mismatched ligands as far as efficiency of the alkylation (entry 2). The use of K+ instead
the configuration of the stereogenic centers is concerned. of Li+ as counterion did not influence the yield or the
The SCRC-configured ligands 39 and 41 provided for a sig- enantioselectivity (entry 3). The Pd-catalyzed reaction of
nificantly higher degree of asymmetric induction than the rac-46 with the malonate anion in the presence of the dia-
corresponding diastereomers 40 and 42. Interestingly, the stereomeric SSSCSC-configured ligand 36 gave malonate
N-tolylsulfonyl and N-silyl-substituted phosphanyl sulfox- (S)-47 in 95% yield with only 73% ee (entry 4). The lower
imines 43 and 44, respectively, gave catalysts of much lower enantioselectivity reflects, as in the case of the acyclic phos-
efficiency in terms of yield and enantioselectivity (entries 5 phanyl sulfoximines, the influence of the chirality of the sulf-
and 6) as compared to those containing the corresponding oximine group on the enantioselectivity. Interestingly, the
phosphanyl N-alkyl sulfoximines as ligands. This can be as- use of the phosphanyl N-benzyl sulfoximine 37 resulted in
cribed to a different mode of coordination of the Pd0 atom a higher enantioselectivity of the reaction of rac-46 with
by the two types of ligands. While the N-alkyl-substituted the malonate anion. With the SSRCRC-configured ligand 37
phosphanyl sulfoximines should have a strong Lewis basic malonate (R)-47 was isolated in 95% yield with 97% ee (en-
N atom, the N-tolylsulfonyl and N-silyl-substituted phos- try 5). In addition, with this ligand the alkylation reaction
phanyl sulfoximines should contain a weak Lewis basic N was much faster than with all other ligands tested so far.
atom.[1] Hence, the former two phosphanyl sulfoximines The reaction was complete at room temperature within
Eur. J. Org. Chem. 2010, 2157–2175
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2163

F. Lemasson, H.-J. Gais, J. Runsink, G. Raabe
FULL PAPER
50 min using 3 mol-% of the catalyst. The reaction of ace- tively, in the presence of ligand 37 proceeded with the same
tate rac-46 with the malonate anion in the presence of the sense of asymmetric induction. The alkylation with the cy-
SSSCSC-configured phosphanyl sulfoximine 38 furnished clic allylic acetate rac-50 in the presence of ligand 37 gave
the S-configured malonate (S)-47 in 96% yield with only after 24 h reaction time the R-configured malonate (R)-51
79% ee (entry 7). These results show that the chiral back- in 70% yield with 36% ee. It is interesting to note that in
bone of the ligand is the key factor determining the the alkylation of the malonate anion with diphenyl- and
enantioselectivity of the alkylation. However, the chirality dialkyl-substituted allylic substrates the cyclic phosphanyl
of the sulfoximine group and the N-substituent also exert a sulfoximine 37 shows in regard to the degree of asymmetric
strong effect.
induction a similar behavior as the [(diphenylphosphanyl)-
phenyl]oxazolines.[10b]
Scheme 9. Cyclic phosphanyl sulfoximines in Pd-catalyzed allylic
alkylation of acetate 46.
Table 6. Pd-catalyzed allylic alkylation of acetate rac-46 with cyclic
phosphanyl sulfoximines as ligand.
Scheme 10. Asymmetric allylic alkylation of acetates rac-48 and
rac-50 using phosphanyl sulfoximine 37 as ligand.
Entry Ligand R1
Config. Ligand/Pd
47
Yield (%) ee% Config.
1
35
35
35
36
37
37
38
38
Me
Me
Me
Me
SSRCRC
SSRCRC
SSRCRC
SSSCSC
1:1
2:1
1:1
1:1
1:1
1:1
1:1
1:1
97
95
96
95
98
96
96
96
86
86
86
73
97
95
79
79
R
R
R
S
R
R
S
2
Mode of Coordination of the Cyclic Phosphanyl
Sulfoximine to the Pd Atom in the π-1,3-Diphenylallyl-PdII
Complex
3[a]
4
5
CH2Ph SSRCRC
CH2Ph SSRCRC
CH2Ph SSSCSC
CH2Ph SSSCSC
6[b]
7
The π-1,3-diphenylallyl-PdII complex 53 containing the
cyclic phosphanyl sulfoximine 37 as ligand was synthesized
upon the successive treatment of the π-1,3-diphenylallyl–
Pd0 complex 52[39] with 1 equiv. of phosphanyl sulfoximine
37 and AgSbF6 (Scheme 11). Complex 53 and phosphanyl
sulfoximine 37 were studied by NMR spectroscopy in order
to reveal the mode of coordination of the phosphanyl sulf-
oximine to the Pd atom. Selected NMR spectroscopic data
of phosphanyl sulfoximine 37 and complex 53 are listed in
8[b]
S
[a] KOAc was used instead of LiOAc. [b] Prepared in situ from the
phosphane–borane with DABCO.
The above discussed alkylation experiments were run
with the pure phosphanyl sulfoximines. Because of their
ready reaction with dioxygen, it was of interest to see
whether the same results in allylic alkylation could be
achieved with a phosphanyl sulfoximine generated in situ
through deboronation of the corresponding phosphane–
borane. Phosphane 37 was generated upon treatment of the
phosphane–borane 29 with DABCO and the crude ligand
was reacted in the standard fashion with Pd2(dba)3·CHCl3,
rac-46 and the nucleophile. The R-configured malonate (R)-
47 was isolated after 1 h reaction time in 96% yield with
95% ee (entry 6). Similar results were obtained by using the
crude diastereomeric SSSCSC-configured phosphanyl sulf-
oximine 38 (entry 8). Thus, the presence of DABCO·BH3
does not impair the activity of the catalyst in the allylic
alkylation investigated.
1
Table 7. The H, 13C and 31P NMR spectra of the free li-
gand 37 were fully assigned by 1H,1H-, 1H,13C- and 31P,13C-
correlation, DEPT and NOE experiments.
Scheme 11. Synthesis of the π-1,3-diphenylallyl-PdII complex 53.
While the signal of Ca of 37 appeared at δ = 59.4 ppm,
Phosphanyl sulfoximine 37, which showed the highest
enantioselectivity in the allylic alkylation of rac-46 with the
malonate anion, was also tested as ligand in the reaction of that of Cb showed up at δ = 29.4 ppm. The chemical shifts
the racemic dimethyl-substituted allylic acetate rac-48 of both signals are typical for sp3-hybridized C atoms in α-
(Scheme 10). The R-configured malonate (R)-49 was iso- position of a sulfoximine and diphenylphosphanyl group,
lated after a reaction time of 3.5 h in 95% yield with 59% respectively. Both the Ca- and Cb atom are coupled with the
ee. Thus, the allylic alkylation with the diphenyl- and di- P atom and their signals appeared as doublets. Characteris-
1
methyl-substituted allylic acetates rac-46 and rac-48, respec- tic shift differences were observed between the 31P, H and
2164
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 2157–2175

Asymmetric Allylic Alkylation
Table 7. Selected 1H, 13C{1H} and 31P{1H} NMR spectroscopic uration of the 1,3-diphenylallyl group because of overlap of
data of phosphanyl sulfoximine 37 and the π-allyl complex 53.
signals. In addition, the NOE experiments were not capable
37[a]
δP
53[b]
δP
to differentiate between the exo and endo orientation of the
allyl group because of the same reason. A complete NMR
spectroscopic characterization of 53 would have required
the synthesis and NMR study of derivatives of the complex
specifically labeled at the various phenyl groups. This effort
was not undertaken, however, mainly because of the rela-
tively low efficiency of ligand 37 in the allylic alkylation of
rac-48 and rac-50 and the wealth of structural information
on 1,3-diphenylallyl-PdII complexes containing other N,P
ligands.[41] Based on the literature data on 1,3-diphenylallyl-
PdII complexes[41] and the preliminary NMR spectroscopic
data of 53 the most likely candidates for the major isomer
of 53 are endo,syn,syn-53 and exo,syn,syn-53, in which the
1,3-diphenylallyl group has the syn,syn-configuration and
adopts either the endo- or exo-configuration relative to the
ligand (Scheme 12). The 31P NMR spectrum of the crude
complex 53 at room temperature exhibited three signals in
a ratio of 96:2:2. Although the minor components were not
Atom
δH
δC
δH
δC
a
b
g
g
π1
π2
π3
P
3.15
4.14
3.97
4.30
–
–
–
59.4(d)
29.4(d)
46.0(s)
5.10
3.12
2.55
3.40
63.8(d)
28.0(d)
47.8(s)
–
–
–
6.80[c] 106(d)
6.60[c] 110
4.11[d] 67
13.1(s)
22.7(s)
Coupling constants
3J(Ha,Hb)
2J(P,Cπ1
3J(Hπ2,Hπ3
3J(P,Hπ1
3J(Hπ2,Hπ3
Ͻ 2
–
–
–
–
11
17
)
)
)
10.4
[d]
)
[d]
[a] In CDCl3. [b] In [D8]THF. [c] Multiplicity could not be deter-
mined. [d] Could not be determined because of signal overlap.
13C NMR spectra of complex 53 and those of the phos- identified, this observation could indicate the presence of
phanyl sulfoximine 37. The 31P signal of complex 53 experi- three isomers of 53, which are in slow equilibrium with each
enced a low-field displacement, which is typical for a P other. Scheme 12 depicts models of endo,syn,syn-53 and ex-
atom coordinated to a Pd atom.[40] While the signal of the o,syn,syn-53 assuming that the six-membered heterocyclic
Ha atom of complex 53 was shifted to low field, that of the ring adopts a chair-like conformation.
Hb atom was displaced to high-field. The signals of Ha and
Hb of complex 53 were assigned by 1H,13C-correlation. The
displacements of the signals of 53 as compared to 37 gave
a first indication of an inversion of the conformation of the
cyclohexane ring of the coordinated ligand. The cyclohex-
ane ring of phosphanyl sulfoximine 37 has a conformation
being close to that of the corresponding phosphane–borane
29 as indicated by the absence of a coupling between Ha
and Hb [3J(Ha,Hb) Ͻ 2 Hz]. Consequently, both the sulfox-
imine and phosphanyl group of the free ligand 37 adopt an
almost axial position. A change of the conformation of the
cyclohexane ring of the ligand upon coordination to the Pd
3
atom in complex 53 is indicated by a J(Ha,Hb) value of
11 Hz for complex 53. This value translates into Ha–Ca–
Scheme 12. Alleged structure of the π-allyl complexes exo,syn,syn-
53 and endo,syn,syn-53 and their proposed reaction with the malon-
ate anion (Nu).
Cb–Hb and S–Ca–Cb–P dihedral angles of approximately
180° and 60°, respectively. Thus, in complex 53 both the
sulfoximine and phosphanyl group occupy an almost equa-
torial position at the cyclohexane ring. The inversion of the
conformation of the cyclohexane is most easily explained
by a coordination of both the sulfoximine and phosphanyl
group in 53 to the Pd atom. Thus, phosphanyl sulfoximine
37 acts as a bidentate ligand for the Pd atom with formation
of a six-membered 1,5-N,P chelate in complex 53. Com-
pound 53 showed the charateristic chemical shifts and cou-
plings expected for the 1,3-diphenylallyl group (cf.
Table 7).[41] Eight different stereoisomers of the π-allyl-Pd
complex 53 are conceivable, depending on the configuration
of the 1,3-diphenylallyl moiety and its orientation relative
to the ligand. These isomers include endo,syn,syn-53,
exo,syn,syn-53, endo,syn,anti-53 and exo,syn,anti-53,
exo,anti,syn-53, endo,anti,syn-53, exo,anti,anti-53 and
endo,anti,anti-53.[42] Unfortunately, the NMR spectroscopic
Complex endo,syn,syn-53 should be thermodynamically
disfavored because of a steric interaction between the
phenyl rings of the allyl and diphenylphosphanyl group.
Thus, the most stable isomer of complex 53 in solution
should be exo,syn,syn-53, in which the 1,3-diphenylallyl
group has the syn,syn-configuration and adopts the steri-
cally less hindered exo-position. The NMR spectroscopic
data revealed the syn-orientation of Hπ2 and the phenyl
group at Cπ3 (cf. Table 7). Although the orientation of Hπ2
and the phenyl group at Cπ1 could not be determined, the
notion of the major isomer of 53 having the syn,anti-config-
uration is less likely.
Selectivity Model
Reaction of exo,syn,syn-53 with the malonate anion at
data of 53 did allow only a partial assignment of the config- the C atom trans to the P atom is expected to be faster
Eur. J. Org. Chem. 2010, 2157–2175
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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2165

F. Lemasson, H.-J. Gais, J. Runsink, G. Raabe
FULL PAPER
0.00 ppm) as internal reference, or to residual solvents signals
(tetrahydrofuran: 1H: δ = 1.73 and 3.58 ppm, 13C: δ = 25.4 and
67.6 ppm; chloroform: 1H: δ = 7.26 ppm, 13C: δ = 77.0 ppm;
CH2Cl2: 1H: δ = 5.32 ppm, 13C: δ = 53.8 ppm) for 1H and 13C
spectra, and to H3PO4 as external reference for 31P spectra. The
coupling constants are given in Hertz. The multiplicity of the sig-
nals was denoted as follow: s = singlet, d = doublet, t = triplet, b
= broad signal, and combinations thereof. Assignment of the peaks
in the 1H NMR spectra was made by GMQCOSY, GNOE, or
GTOCSY experiments. Assignment of the peaks in the 13C NMR
than that of endo,syn,syn-53 at this position. Attack of the
nucleophile at the C atom of endo,syn,syn-53 in trans posi-
tion to the P atom should be hampered because of steric
interactions between the phenyl rings of (1) the allyl and
phosphanyl group and (2) the benzyl and allyl group. This
model is based on the assumptions that (1) the attack of
the nucleophile at the allylic C atom in trans-position to the
P atom is kinetically preferred and (2) the more stable com-
plex is the most reactive one. While such a preference for
a trans-P-attack had been generally observed in π-allyl-Pd spectra was made by APT, DEPT and HETCOR experiments. IR
complexes containing other N,P ligands,[43] an unidentified
minor isomer of 53 could in principle be more reactive.
spectra were recorded on a Perkin–Elmer PE 1760 FT spectrometer
as KBr pellets or in solution. Absorptions are given in cm–1 in a
range of 4000 to 850 cm–1, and the following abbreviations are used
to describe their relative intensity: w = weak, m = medium, s =
strong. Mass spectra were recorded on a Varian Mat 212 S and
Finnigan MAT 312 for ionization through EI (Electronic impact,
Conclusions
70 eV) and CI (chemical ionization, 100 eV). ESI (electrospray ion-
ization) and ESI-MS/MS were recorded on a Thermo Finnigan
LCQ DECA XPlus instrument. Only peaks of m/z Ͼ 80 and an
intensity Ͼ 10%, except decisive ones, are given. High resolution
mass spectrometry (HRMS) was done with a Finnigan MAT 95
(EI) or Micromass LCT (LC-TOF-HRMS, column Acquit UPLC
The PMR of the substituted cyclic and acyclic alkenyl
sulfoximines with HPPh2/tBuOK proceeded readily and
gave the corresponding phosphanyl sulfoximines in high
yield. The sulfoximine group apparently provides only a low
asymmetric induction in the addition of the P-nucleophile
to the double bond. The cyclic phosphanyl sulfoximines are
efficient ligands in the Pd-catalyzed asymmetric allylic alkyl-
ation of 1,3-diphenylallyl acetate with the malonate anion.
However, the enantioselectivity of the allylic alkylation of
alkyl-substituted allylic acetates with these ligands was only
medium. The cyclohexane ring of the cyclic phosphanyl
sulfoximines undergoes upon coordination of the ligand to
the Pd atom an inversion, which brings the sulfoximine and
phosphanyl group from a pseudo-axial position in the free
ligand to a pseudo-equatorial position in the coordinated
ligand. Formation of a 1,5-N,P chelate is the driving force
for this conformational change.
BEH C18) intrument. Analytical HPLC were performed with Milli-
pore Waters (UV-481) and Hewlett–Packard HP 1050 instruments.
Elemental analyses were done with a Heraeus CHN-Rapid instru-
ment. Optical rotations were measured with a Perkin–Elmer Polari-
meter PE 241 and given in gradϫmL/dmϫg, and the concentra-
tion c in g/100 mL. The measurements were run at approximately
22 °C. Melting points were measured in an open glass capillary
using a Büchi 510 melting point apparatus SMP-20 and are uncor-
rected.
General Procedure for the Preparation of Acyclic Alkenyl Sulfox-
imines (Method A). (+)-(E)-{2-[(S)-N-Benzyl-S-phenylsulfon-
imidoyl]alkenyl}benzene (7): In a round-bottom Schlenk flask, sulf-
oximine 3 (2.30 g, 9.38 mmol) was dissolved in anhydrous THF
(30 mL) and the mixture was cooled to –78 °C. A solution of nBuLi
(16.45 mL, 10.32 mmol) was added dropwise to the mixture, and
the resulting yellow mixture was stirred for 30 min. Benzaldehyde
(1.10 g, 10.32 mmol) was added within 5 min and the colorless mix-
ture was stirred at the same temperature for 1 h. Then the mixture
was treated with ClCO2Me (980 mg, 10.32 mmol) and it was
warmed to room temperature. After the mixture was stirred for 1 h,
it was cooled to –78 °C and DBU (1.57 g, 10.32 mmol) was added
dropwise. The mixture was warmed to room temperature and it
was stirred overnight. The heterogeneous mixture was quenched
with saturated aqueous NH4Cl and extracted with EtOAc
(4ϫ30 mL). The combined organic phases were dried (MgSO4)
and concentrated in vacuo. Purification by column chromatog-
raphy (cyclohexane/EtOAc, 85:15) afforded the alkenyl sulfoximine
7 (3.84 g, 91%) as pale yellow solid. Crystallization by layering n-
hexane on the top of a saturated solution of the crude mixture in
CH2Cl2 afforded 7 as fine white needles; m.p. 101 °C. [α]D = +24.0
Experimental Section
Experimental Procedures: Reactions involving dioxygen and water
sensitive compounds were carried out under an argon or nitrogen
atmosphere using standard Schlenk, cannula and syringe tech-
niques in oven-dried glassware. Sulfoximine 1 was prepared accord-
ing to the literature.[19,44] All reagents employed were obtained from
commercial suppliers. tBuOK was purified by sublimation and
benzaldehyde by distillation. Diisopropylamine was distilled from
CaH2. nBuLi was received as a 1.6  solution in n-hexane and stan-
dardized using either diphenylacetic acid or phenanthroline and
benzyl alcohol. BH3·THF was received as a 1  solution in THF.
All other chemicals were used as received without further purifica-
tion. Toluene was distilled from sodium, and CH2Cl2 was distilled
from CaH2. THF and Et2O were distilled from sodium-benzophe-
none ketyl. All anhydrous solvents were degassed via three freeze-
thaw cycles and stored in a Schlenk flask closed with two Glinde-
mann® sealings and PARAFILM®M. Flash column chromatog-
raphy was performed on E. Merck silica gel 60, 0.040–0.063 mm.
Thin layer chromatography (TLC) was performed on E-Merck pre-
1
(c = 1.00, CH2Cl2). H NMR (CDCl3, 300 MHz): δ = 4.22 (d, J =
14.6 Hz, 1 H, NCH2), 4.35 (d, J = 14.6 Hz, 1 H, NCH2), 6.88 (d,
J = 15.3 Hz, 1 H, SCH), 7.22 (m, 1 H, Ar), 7.34 (m, 5 H, Ar), 7.44
(m, 4 H, Ar), 7.56 (m, 4 H, Ar and S-CH=CH), 8.01 (m, 2 H, Ar)
coated alumina sheets (silica gel 60 F254). Development of TLC ppm. 13C NMR (CDCl3, 75 MHz): δ = 47.2 (CH2), 126.5 (CH),
was done either by UV-light (λ = 254 nm) or p-anisaldehyde, phos-
127.6 (CH), 127.8 (CH), 128.3 (CH), 128.4 (CH), 128.7 (CH), 129.0
(CH), 129.3 (CH), 130.8 (CH), 132.7 (CH), 132.8 (C), 140.1 (C),
1
phomolybdic acid, potassium permanganate and/or ninhydrin. H,
13C and 31P NMR spectra were recorded on Varian (Gemini 300,
Mercury 300, Inova 400) instruments. Chemical shifts are given in
ppm relative to tetramethylsilane (1H: δ = 0.00 ppm, 13C: δ =
141.5 (C), 142.6 (CH) ppm. IR (KBr): ν = 2882 (s), 1240 (s), 1122
˜
(s), 1074 (s) cm–1. MS (CI, CH4): m/z (%) = 334 (100) [M+ + 1],
229 (13), 208 (12), 91 (10). HRMS: calcd. for C21H19NOS:
2166
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 2157–2175

Asymmetric Allylic Alkylation
333.1187; found 333.1188. C21H19NOS (333.4): calcd. C 75.64,
H 5.74, N 4.20; found C 75.70, H 5.71, N 4.19.
motetrachloroethane (490 mg, 1.50 mmol) in anhydrous THF
(2 mL) was added dropwise. After the mixture was stirred for
45 min, it was warmed to room temperature and stirred overnight.
Then the mixture was quenched with saturated aqueous NH4Cl,
and the aqueous layer was extracted with Et2O (4ϫ 5 mL). The
combined organic phases were dried (MgSO4) and concentrated in
vacuo. Purification by column chromatography (cyclohexane/
EtOAc, 85:15) afforded a mixture of the chloro sulfoximine 11 and
bromo sulfoximine 12 (202 mg, 91%) in a ratio 45:55. GC: Rt(11)
(+)-(E)-{2-[(S)-N-Methyl-S-phenylsulfonimidoyl]alkenyl}benzene
(6): According to method A, the alkenyl sulfoximine 6 was pre-
pared starting from sulfoximine 2 (4.05 g, 23.93 mmol), nBuLi
(16.45 mL, 26.29 mmol), benzaldehyde (2.79 g, 26.29 mmol),
ClCO2Me (2.49 g, 26.29 mmol) and DBU (4.00 g, 26.29 mmol) in
THF (60 mL). Purification by column chromatography (cyclohex-
ane/EtOAc, 3:2) afforded the alkenyl sulfoximine 6 (5.42 g, 88%)
1
= 10.6 min, Rt(12) = 11.1 min. H NMR (300 MHz, CDCl3): δ =
1
as colorless oil, which crystallized at –26 °C. H NMR (300 MHz,
1.22 (m, 1 H), 1.60–1.80 (m, 6 H), 1.90–2.40 (m, 4 H), 2.80 (s)/2.81
(s, 3 H), 7.53–7.70 (m, 3 H), 7.90–8.00 (m, 2 H) ppm. 13C NMR
(75 MHz, CDCl3): δ = 21.6 (CH2), 21.7 (CH2), 22.5 (CH2), 24.3
(CH2), 30.1 (CH3), 30.3 (CH3), 32.3 (CH2), 33.38 (CH2), 33.42
(CH2), 34.5 (CH2), 86.8 (C), 89.6 (C), 128.6 (CH), 128.7 (CH),
132.2 (CH), 132.3 (CH), 133.1 (CH), 133.2 (CH), 133.3 (C) ppm.
CDCl3): δ = 2.81 (s, 3 H, NCH3), 6.88 (d, J = 15.3 Hz, 1 H, SCH),
7.37 (m, 3 H, CH-m-Ph and CH-p-Ph), 7.47 (m, 2 H, CH-o-Ph),
7.50–7.62 (m, 4 H, S-o-Ph and S-p-Ph and S-CH=CH), 7.96 (m, 2
H, S-m-Ph) ppm. 13C NMR (75 MHz, CDCl3): δ = 29.5 (CH3,
NCH3), 127.4 (CH, S-CH), 128.4 (CH), 128.7 (CH), 129.0 (CH),
129.4 (CH) (CH-o-Ph, CH-m-Ph, S-o-Ph and S-m-Ph), 130.8 (CH),
132.7 (CH) (CH-p-Ph and S-p-Ph), 132.8 (C, CH-i-Ph), 139.4 (C,
S-i-Ph), 142.6 (CH, S-CH=CH) ppm.
11: GC–MS (EI): m/z (%) = 118 (15), 116 (35), 81 (100).
12: GC–MS (EI): m/z (%) = 162 (17), 160 (17), 81 (100).
(–)-(E)-{2-[(S)-N-(p-Tolylsulfonyl)-S-phenylsulfonimidoyl]alkenyl}-
benzene (8): According to method A, the alkenyl sulfoximine 8 was
prepared starting from sulfoximine 4 (6.80 g, 22.0 mmol), nBuLi
(15.3 mL, 24.2 mmol), benzaldehyde (2.57 g, 24.2 mmol),
ClCO2Me (2.28 g, 24.2 mmol) and DBU (3.69 g, 24.2 mmol) in
THF (60 mL). Purification by column chromatography (cyclohex-
ane/EtOAc/CH2Cl2, 13:6:1) afforded the alkenyl sulfoximine 8
(5.42 g, 88%) as white solid. 1H NMR (300 MHz, CDCl3): δ = 2.36
(s, 3 H, Ph-CH3), 6.90 (d, J = 15.1 Hz, S-CH), 7.23 (m, 2 H, Ph),
7.34–7.47 (m, 4 H, Ph), 7.52–7.67 (m, 5 H, Ph and S-CH=CH),
7.86 (m, 2 H), 8.01 (m, 2 H, Ph) ppm. 13C NMR (75.4 MHz,
CDCl3): δ = 21.5 (CH3), 125.5 (CH), 126.8 (CH), 127.7 (CH), 128.9
(CH), 129.1 (CH), 129.3 (CH), 129.6 (CH), 131.7 (CH), 131.8 (C),
134.0 (CH), 138.7 (C), 140.8 (C), 142.8 (C), 143.9 (CH) ppm.
(S,E)-(N-Methyl-6-bromohex-1-enylsulfonimidoyl)benzene (15): Ac-
cording to method A, the alkenyl sulfoximine 15 was prepared
starting from sulfoximine 2 (540 mg, 3.19 mmol), nBuLi (2.19 mL,
3.50 mmol), 5-bromopentanal (580 mg, 3.51 mmol), ClCO2Me
(332 mg, 3.51 mmol) and DBU (486 mg, 3.51 mmol). Purification
by column chromatography (cyclohexane/EtOAc, 3:2) afforded a
pale yellow oil consisting of the alkenyl sulfoximine 15 (2.65 g,
83%) and an unidentified side product. 1H NMR (300 MHz,
CDCl3): δ = 1.63 (m, 2 H, CHCH2CH2), 1.85 (m, 2 H, BrCH2CH2),
2.27 (m, 2 H, CHCH2), 2.73 (s, 3 H, NCH3), 3.38 (t, J = 6.8 Hz, 2
H, BrCH2), 6.34 (dt, J = 15.1, J = 1.7 Hz, 1 H, SCH), 6.85 (dt, J
= 15.1, J = 6.8 Hz, 1 H, SCHCH), 7.56 (m, 3 H, S-o-Ph and S-p-
Ph), 7.87 (m, 2 H, S-m-Ph) ppm. 13C NMR (75 MHz, CDCl3): δ =
26.2 (CH2, CHCH2CH2), 29.4 (CH3, NCH3), 30.5 (CH2, CHCH2),
32.0 (CH2, BrCH2CH2), 33.0 (CH2, BrCH2), 128.7 (CH, S-m-Ph),
129.3 (CH, S-o-Ph), 130.8 (CH, SCH), 132.6 (CH, S-p-Ph), 139.3
(C, S-i-Ph), 145.7 (CH, SCH=CH) ppm.
(–)-(E)-{2-[(S)-N-(tert-Butyldiphenylsilyl)-S-phenylsulfonimidoyl]-
alkenyl}benzene (9): According to method A, the alkenyl sulfoxim-
ine
9 was prepared starting from sulfoximine 5 (6.00 g,
15.24 mmol), nBuLi (10.5 mL, 16.77 mmol), benzaldehyde (1.78 g,
16.77 mmol), ClCO2Me (1.59 g, 16.77 mmol) and DBU (2.55 g,
16.77 mmol). Purification by column chromatography (cyclohex-
ane/EtOAc, 12:1) afforded the alkenyl sulfoximine 9 (6.23 g, 85%)
as colorless oil, which solidified upon standing at 4 °C. White solid;
(S,E)-(N-Benzyl-6-bromohex-1-enylsulfonimidoyl)benzene (16): Ac-
cording to method A, the alkenyl sulfoximine 16 was prepared
starting from sulfoximine 3 (4.32 g, 17.6 mmol), nBuLi (12.1 mL,
19.3 mmol), 5-bromopentanal (3.19 g, 19.3 mmol), ClCO2Me
(1.83 g, 19.3 mmol) and DBU (2.89 mL, 19.7 mmol). Purification
by column chromatography (cyclohexane/EtOAc, 3:1) afforded a
pale yellow oil consisting of the alkenyl sulfoximine 16 (5.0 g, 77%)
1
m.p. 69 °C. [α]D = –62.3 (c = 1.30, CH2Cl2). H NMR (300 MHz,
CDCl3): δ = 1.13 [s, 9 H, C(CH3)3], 6.63 (d, J = 15.2 Hz, 1 H,
SCH), 7.19 (m, 2 H, Ph), 7.28 (m, 9 H, Ph), 7.42 (m, 4 H, Ph and
S-CH=CH), 7.75 (m, 4 H, Ph), 7.93 (m, 2 H, Ph) ppm. 13C NMR
(75 MHz, CDCl3): δ = 19.5 (C), 27.2 (CH3), 127.32 (CH), 127.34
(CH), 127.36 (CH), 128.2 (CH), 128.7 (CH), 128.8 (CH), 128.91
(CH), 128.93 (CH), 130.2 (CH), 131.8 (CH), 132.0 (CH), 132.9 (C),
135.61 (CH), 135.64 (CH), 136.3 (C), 136.4 (C), 138.8 (CH), 144.3
1
and an unidentified side product. H NMR (400 MHz, CDCl3): δ
= 1.49 (m, 2 H, CHCH2CH2), 1.82 (m, 2 H, BrCH2CH2), 2.23 (m,
2 H, CHCH2), 3.35 (t, J = 6.6 Hz, 2 H, BrCH2), 4.12 (d, J =
14.6 Hz, 1 H, NCH2), 4.26 (d, J = 14.6 Hz, 1 H, NCH2), 6.37 (dt,
J = 15.1, J = 1.4 Hz, 1 H, SCH), 6.88 (dt, J = 15.1, J = 6.6 Hz, 1
H, SCHCH), 7.20 (m, 1 H, NCH2-p-Ph), 7.29 (m, 2 H, NCH2-m-
Ph), 7.38 (m, 2 H, NCH2-o-Ph), 7.54 (m, 3 H, S-o-Ph and S-p-Ph),
7.91 (m, 2 H, S-m-Ph) ppm. 13C NMR (100 MHz, CDCl3): δ =
25.7 (CH2, CHCH2CH2), 30.4 (CH2, CHCH2), 31.8 (CH2,
BrCH2CH2), 33.0 (CH2, BrCH2), 47.0 (CH2, NCH2), 126.3 (CH,
NCH2-p-Ph), 127.3 (CH, NCH2-m-Ph), 128.0 (CH, NCH2-o-Ph),
128.4 (CH, S-m-Ph), 129.5 (CH, S-o-Ph or S-p-Ph), 130.8 (CH, S-
CH), 132.4 (CH, S-o-Ph or S-p-Ph), 139.6 (C, S-i-Ph), 141.2 (C,
NCH2-i-Ph), 145.6 (CH, S-CH=CH) ppm. MS (CI, CH4): m/z (%)
= 394 (88), 392 (100) [M+ + 1], 390 (10), 350 (16), 349 (11), 348
(46), 312 (13), 268 (11), 266 (13), 125 (13), 91 (20).
(C) ppm. IR (KBr): ν = 3048 (m), 2952 (m), 2928 (m), 2887 (m),
˜
2853 (m), 1616 (m), 1578 (w), 1472 (w), 1445 (m), 1425 (m), 1390
(w), 1283 (s), 1185 (w), 1140 (s), 1103 (s), 1025 (m), 999 (w), 965
(m), 870 (m), 820 (s) cm–1. MS (CI, CH4): m/z (%) = 482 (16) [M+
+ 1], 425 (11), 424 (34), 406 (10), 405 (29), 404 (100), 105 (17), 61
(11). HRMS: calcd. for C26H22NOSSi [M+ – C4H9]: 424.1191;
found 424.1195. C30H31NOSSi (481.19): calcd. C 74.80, H 6.49,
N 2.91; found C 74.83, H 6.78, N 2.76.
{1-Chlorocyclohexyl[(S)-N-methylsulfonimidoyl]}benzene (11) and
{1-Bromocyclohexyl[(S)-N-methylsulfonimidoyl]}benzene (12): In a
round-bottom Schlenk flask, sulfoximine 10 (178 mg, 750 µmol)
was dissolved in anhydrous THF (2 mL). The solution was cooled
to –15 °C and nBuLi (0.51 mL, 816 µmol) was added dropwise. The
yellow mixture was stirred for 30 min and a solution of 1,2-dibro-
General Procedure for the Preparation of Cyclic Alkenyl Sulfox-
imines (Method B). (+)-(S)-[N-Methyl-(S-cyclohex-1-ene)sulfon-
imidoyl]benzene (17): In a round-bottom Schlenk flask, freshly dis-
Eur. J. Org. Chem. 2010, 2157–2175
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2167

F. Lemasson, H.-J. Gais, J. Runsink, G. Raabe
FULL PAPER
tilled diisopropylamine (1.91 mL, 13.73 mmol) was dissolved in an-
hydrous THF (450 mL). The solution was cooled to –78 °C and
nBuLi (8.58 mL, 13.73 mmol) was added dropwise. After the mix-
ture was stirred for 15 min, it was warmed to room temperature
for 5 min and then cooled to –78 °C. A solution of 6-bromosulfox-
imine 15 (4.21 g, 13.31 mmol) in THF (450 mL), which was pre-
viously cooled to –78 °C, was added to the solution of LDA within
5 min via a double-ended cannula. After the yellow mixture was
stirred for 40 min, it was warmed to 0 °C. Then the mixture was
quenched with saturated aqueous NH4Cl. The organic layer was
separated, and the aqueous layer was extracted with EtOAc (4ϫ
300 mL). The combined organic phases were dried (MgSO4) and
concentrated in vacuo. Purification by column chromatography
(cyclohexane/EtOAc, 3:2) afforded the alkenyl sulfoximine 17
(2.50 g, 80%) as white solid; m.p. 49 °C. [α]D = +31.1 (c = 0.26,
Et2O). 1H NMR (400 MHz, CDCl3): δ = 1.47–1.70 (m, 4 H, CH2),
2.06 (m, 1 H, CH2), 2.22–2.38 (m, 3 H, CH2), 2.76 (s, 3 H, NCH3),
7.02 (m, 1 H, SCCH), 7.53 (m, 3 H, Ph), 7.86 (m, 2 H, Ph) ppm.
13C NMR (100 MHz, CDCl3): δ = 20.9 (CH2), 22.1 (CH2), 23.6
(CH2), 25.7 (CH2), 29.4 (CH3), 128.80 (CH), 128.82 (CH), 132.1
The combined organic phases were dried (MgSO4) and concen-
trated in vacuo. A mixture of the diastereomeric phosphane–
boranes 19 and 20 in a ratio of 78:22 [Chiral OD-H column, detec-
tor 254 nm, n-heptane/2-propanol, 98:2, flow: 0.75 mL/min, 36 bar,
Rt(19) = 22.4 min; Rt(20) = 27.1 min] was obtained. Purification
by column chromatography (cyclohexane/EtOAc, 4:1) afforded the
phosphane–borane 20 (122 mg, 17%) as white foam and phos-
phane–borane 19 (430 mg, 61%) as white crystalline solid. Layer-
ing n-hexane on the top of a saturated solution of a mixture of
both isomers in CH2Cl2 gave the phosphane–borane 19 as colorless
single crystals suitable for X-ray analysis.
19: M.p. 117 °C. [α]D = –116.5 (c = 1.19, CH2Cl2). 1H NMR
(300 MHz, CDCl3): δ = 0.4–1.4 (br. s, 3 H, BH3), 2.51 (s, 3 H,
3
NCH3), 3.63 (ddd, J = 15.1, JP,H = 10.2, J = 1.6 Hz, 1 H, SCH2),
3
4.06 (ddd, J = 15.1, J = 11.8, JP,H = 1.9 Hz, 1 H, SCH2), 4.46
2
(ddd, JP,H = 15.1, J = 11.8, J = 1.6 Hz, 1 H, SCH2CH), 6.79 (m,
4 H), 6.89 (m, 1 H), 7.13–7.23 (m, 6 H), 7.29 (m, 2 H), 7.37 (m, 2
H), 7.59 (m, 3 H), 8.01 (m, 2 H) ppm. 13C NMR (75 MHz, CDCl3):
1
δ = 29.3 (CH3, NCH3), 38.0 [d, J(P,C) = 28.8 Hz, CH, SCH2CH],
2
1
56.7 (d, JP,C = 7.9 Hz, CH2, SCH2), 125.9 (d, JP,C = 51.6 Hz, 1
(CH), 138.0 (C), 138.2 (CH), 138.5 (C) ppm. IR (KBr): ν = 3060
˜
1
C, i-Ph), 127.0 (d, JP,C = 54.9 Hz, 1 C, i-Ph), 127.3 (d, JP,C
=
(w), 2935 (s), 2867 (m), 2801 (m), 1444 (s), 1341 (w), 1244 (s), 1148
(s), 1110 (m), 1081 (m), 1048 (w), 1022 (w), 937 (m), 864 (m) cm–1.
MS (CI, CH4): m/z (%) = 236 (18) [M+ + 1], 235 (93) [M+], 234
(10), 139 (11), 129 (11), 126 (11), 125 (25), 110 (100), 109 (16), 97
(13), 81 (58), 80 (6), 79 (45), 78 (19), 77 (33), 69 (15), 68 (18).
HRMS: calcd. for C13H17NOS: 235.1031; found 235.1031.
2.4 Hz, CH), 127.6 (d, JP,C = 1.9 Hz, CH), 128.2 (d, JP,C = 10.1 Hz,
CH), 128.9 (CH), 129.1 (CH), 129.4 (d, JP,C = 9.7 Hz, CH), 130.0
(d, JP,C = 4.2 Hz, CH), 131.2 (d, JP,C = 1.7 Hz, CH), 131.8 (C),
132.1 (d, JP,C = 1.8 Hz, CH), 132.4 (CH), 132.5 (d, JP,C = 8.8 Hz,
CH), 133.2 (d, JP,C = 8.6 Hz, CH), 136.8 (C) ppm. 31P NMR
(162 MHz, CDCl ): δ = 25.48 (br. s) ppm. IR (KBr): ν = 3908 (w),
˜
3
3654 (w), 3465 (m), 3055 (m), 2974 (w), 2932 (m), 2871 (m), 2802
(m), 2383 (s), 2348 (s), 2274 (w), 1583 (w), 1491 (m), 1438 (m),
1403 (w), 1267 (m), 1236 (s), 1142 (s), 1104 (s), 1064 (s), 997 (w),
916 (m), 855 (s), 823 (m) cm–1. MS (CI, CH4): m/z (%) = 456 (1)
[M+ + 1], 300 (23), 299 (100), 298 (24), 289 (11), 184 (14), 156 (54),
125 (28). C27H29BNOPS (457.38): calcd. C 70.90, H 6.39, N 3.06;
found C 71.04, H 6.51, N 2.86.
(–)-(S)-[N-Benzyl-(S-cyclohex-1-ene)sulfonimidoyl]benzene (18): Ac-
cording to method B, the cycloalkenyl sulfoximine 18 was prepared
starting from 6-bromosulfoximine 16 (3.73 g, 9.51 mmol) in THF
(330 mL), diisopropylamine (1.37 mL, 9.70 mmol) and nBuLi
(6.06 mL, 9.70 mmol) in THF (240 mL). Purification by column
chromatography (cyclohexane/EtOAc, 85:15) afforded the alkenyl
sulfoximine 18 (2.74 g, 92%) as white solid; m.p. 61–62 °C. [α]D
=
–0.80 (c = 1.0, CHCl3). 1H NMR (300 MHz, CDCl3): δ = 1.45–
170 (m, 4 H, CH2), 2.08 (m, 1 H, CH2), 2.20–2.41 (m, 3 H, CH2),
4.18 (d, J = 14.9 Hz, 1 H, NCH2), 4.27 (d, J = 14.9 Hz, 1 H,
NCH2), 7.09 (m, 1 H, SCCH), 7.21 (m, 1 H, NCH2Ph), 7.30 (m, 2
H, NCH2Ph), 7.41–7.60 (m, 5 H, SPh and NCH2Ph), 7.91 (m, 2
H, SPh) ppm. 13C NMR (75 MHz, CDCl3): δ = 20.9 (CH2), 22.2
(CH2), 23.7 (CH2), 25.8 (CH2), 46.9 (CH2), 126.3 (CH), 127.4
(CH), 128.1 (CH), 128.99 (CH), 129.00 (CH), 132.4 (CH), 138.63
20: M.p. 53–55 °C. [α]D = +142.9 (c = 1.80, CH2Cl2). 1H NMR
(300 MHz, CDCl3): δ = 0.3–1.4 (br. s, 3 H, BH3), 2.61 (s, 3 H,
3
NCH3), 3.54 (ddd, J = 14.9, JP,H = 10.3, J = 1.5 Hz, 1 H, SCH2),
3
3.98 (ddd, J = 14.9, J = 11.8, JP,H = 1.9 Hz, 1 H, SCH2), 4.39
2
(ddd, JP,H = 16.3, J = 11.8, J = 1.3 Hz, 1 H, SCH2CH), 6.88 (m,
2 H), 6.92 (m, 2 H), 7.04 (m, 1 H), 7.14–7.34 (m, 7 H), 7.37–7.60
(m, 6 H), 7.87 (m, 2 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
1
29.4 (CH3, NCH3), 38.9 (d, JP,C = 28.7 Hz, CH, SCH2CH), 56.7
(C), 138.74 (CH), 138.86 (C), 141.8 (C) ppm. IR (KBr): ν = 3379
˜
2
1
(d, JP,C = 8.0 Hz, CH2, SCH2), 125.9 (d, JP,C = 51.6 Hz, 1 C, i-
(w), 3062 (m), 3021 (w), 2934 (s), 2859 (m), 1641 (w), 1491 (w),
1445 (m), 1352 (w), 1257 (s), 1135 (s), 1078 (m), 1024 (w), 909 (m)
cm–1. MS (CI, isobutane): m/z (%) = 312 (100) [M+ + 1]. HRMS:
calcd. for C19H21NOS: 311.1344; found 311.1345.
1
Ph), 127.1 (d, JP,C = 56.0 Hz, 1 C, i-Ph), 127.5 (d, JP,C = 2.9 Hz,
CH), 127.7 (d, JP,C = 2.4 Hz, CH), 128.2 (d, JP,C = 10.1 Hz, CH),
128.9 (CH), 129.1 (CH), 129.7 (d, JP,C = 9.2 Hz, CH), 130.0 (d,
JP,C = 4.3 Hz, CH), 131.2 (d, JP,C = 2.4 Hz, CH), 131.9 (d, JP,C
=
2.4 Hz, CH), 132.4 (C), 132.5 (CH), 132.6 (d, JP,C = 8.8 Hz, CH),
General Procedure for the Preparation of Phosphane–Boranes
(Method C). (+)-Diphenyl{(1S)-1-phenyl-2-[(S)-N-methyl-S-phenyl-
sulfonimidoyl]ethyl}phosphane–Borane (20) and (–)-Diphenyl{(1R)-
1-phenyl-2-[(S)-N-methyl-S-phenylsulfonimidoyl]ethyl}phosphane–
Borane (19): In a round-bottom Schlenk flask, the alkenyl sulfox-
imine 6 (400 mg, 1.55 mmol) was dissolved in anhydrous and degassed
THF (12 mL). Then diphenylphosphane (335 mg, 1.70 mmol) and
tBuOK (17 mg, 170 µmol) were successively added at room tem-
perature. The mixture was stirred at room temperature until TLC
indicated a complete conversion of the alkenyl sulfoximine 6 (1 to
2 h). Then the mixture was cooled to 0 °C and BH3·THF (3.41 mL,
3.41 mmol) was added dropwise. The mixture was warmed to room
temperature and after 1 h it was cooled to 0 °C. 1  H2SO4 (CAU-
TION: gas evolution) was added carefully until a pH of 5 was
reached. Then the mixture was extracted with CH2Cl2 (3ϫ20 mL).
133.2 (d, JP,C = 8.5 Hz, CH), 138.0 (C) ppm. 31P NMR (162 MHz,
CDCl ): δ = 26.11 (br. s) ppm. IR (KBr): ν = 3460 (w), 2922 (m),
˜
3
2805 (w), 2375 (s), 1971 (w), 1900 (w), 1814 (w), 1673 (w), 1585
(m), 1483 (m), 1438 (s), 1245 (s), 1128 (s), 1063 (s), 915 (m), 855
(w) cm–1. MS (ESI-MS, MeOH): m/z (%) = 458 (100) [M+ + 1],
443 (28), 333 (12), 319 (24), 305 (32), 299 (44), 289 (38), 156 (28).
C27H29BNOPS (457.38): calcd. C 70.90, H 6.39, N 3.06; found
C 71.01, H 6.36, N 3.06.
(–)-Diphenyl{(1R)-1-phenyl-2-[(S)-N-benzyl-S-phenylsulfonimidoyl]-
ethyl}phosphane–Borane (21) and (+)-Diphenyl{(1S)-1-phenyl-2-
[(S)-N-benzyl-S-phenylsulfonimidoyl]ethyl}phosphane–Borane (22):
According to method C, the phosphane–boranes 21 and 22 were
prepared starting from the alkenyl sulfoximine 7 (700 mg,
2.10 mmol), diphenylphosphane (453 mg, 2.31 mmol) and tBuOK
2168
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Eur. J. Org. Chem. 2010, 2157–2175

Asymmetric Allylic Alkylation
(22 mg, 0.21 mmol) in THF (18 mL). After the complete conver-
sion of sulfoximine 7, BH3·THF (4.62 mL, 4.62 mmol) was added.
Work up after the mixture was stirred for 1 h gave a mixture of 21
and 22 in a ratio of 64:36 [chiralpack-IA column, detector 230 nm,
n-heptane/2-propanol, 85:15, flow: 0.75 mL/min, 32 bar, Rt(22) =
14.90 min; Rt(21) = 21.28 min]. Purification by column chromatog-
raphy (cyclohexane/EtOAc, 85:15) afforded the phosphane–borane
boranes 24 and 23 were prepared starting from alkenyl sulfoximine
8 (2.0 g, 5.03 mmol), diphenylphosphane (1.03 g, 5.5 mmol) and
tBuOK (56 mg, 500 µmol) in THF (60 mL). After the complete
conversion of sulfoximine 8, BH3·THF (11 mL, 11 mmol) was
added. Work up after the mixture was stirred for 1 h gave a mixture
of 24 and 23 in a ratio of 73:27 [Kromasil Si 100 column, detector
254 nm, cyclohexane/EtOAc/CH2Cl2, 11:2:0.5, flow: 1 mL/min,
21 (592 mg, 53%) as white crystalline solid and the phosphane– 30 bar, Rt(23) = 8.49 min; Rt(24) = 11.07 min]. The crude mixture
borane 22 (277 mg, 25%) as white foam. Layering n-hexane on the
top of a saturated solution of both isomers in CH2Cl2 gave the
phosphane–borane 21 as fine white needles.
was dissolved in CH2Cl2 and silica gel was added before the evapo-
ration so that the crude mixture was adsorbed on silica gel. The
loaded silica gel was placed on top of a column containing silica
gel. Purification by column chromatography (cyclohexane/EtOAc/
CH2Cl2, 11:2:1) afforded in the first collected fractions the phos-
phane–borane 23, which was contaminated with the phosphane–
borane 24. After evaporation of the solvents, the residue was dis-
solved in the minimum amount of CH2Cl2 and n-hexane was lay-
ered on the top of the saturated solution. The phosphane–borane
23 crystallized at –26 °C as colorless needles (540 mg, 18%). The
major isomer was eluted with CHCl3 to yield the phosphane–
borane 24, which was contaminated with the phosphane–borane
23. After evaporation of the solvents, the residue was dissolved in
the minimum amount of CH2Cl2 and n-hexane was layered on the
top of the saturated solution. The phosphane–borane 24 crys-
tallized in CH2Cl2 at 4 °C as woolly solid (1.53 g, 51%).
21: M.p. 140 °C. [α]D = –140.3 (c = 1.03, CHCl3). 1H NMR
(400 MHz, CDCl3): δ = 0.4–1.5 (br. s, 3 H, BH3), 3.70 (ddd, J =
3
14.8, JP,H = 10.1, J = 1.4 Hz, 1 H, SCH2), 3.98 (d, J = 14.6 Hz, 1
H, NCH2Ph), 4.04 (d, J = 14.6 Hz, 1 H, NCH2Ph), 4.08 (ddd, J =
14.8, J = 11.8, 3JP,H = 1.8 Hz, 1 H, SCH2), 4.54 (ddd, 2JP,H = 16.7,
J = 11.8, J = 1.4 Hz, 1 H, SCH2CH), 6.83 (m, 4 H), 6.93 (m, 1 H),
7.13–7.35 (m, 13 H), 7.44 (m, 2 H), 7.53–7.63 (m, 3 H), 8.01 (m, 2
1
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 37.9 (d, JP, C
=
=
2
29.8 Hz, CH, SCH2CH), 46.9 (CH2, NCH2Ph), 56.3 (d, JP,C
1
8.4 Hz, CH2, SCH2), 125.8 (d, JP,C = 51.9 Hz, 1 C, i-Ph), 126.3
(CH), 127.0 (d, JP,C = 54.2 Hz, 1 C, i-Ph), 127.10 (CH), 127.13
1
(CH), 127.4 (d, JP,C = 2.3 Hz, CH), 128.0 (CH), 128.3 (d, JP,C
=
9.9 Hz, CH), 128.7 (CH), 128.8 (CH), 129.1 (d, JP,C = 9.9 Hz, CH),
129.7 (d, JP,C = 4.6 Hz, CH), 130.9 (d, JP,C = 2.3 Hz, CH), 131.82
(C), 131.85 (CH), 132.2 (CH), 132.3 (d, JP,C = 9.1 Hz, CH), 133.0
(d, JP,C = 9.1 Hz, CH), 137.5 (C),141.0 (C) ppm. 31P NMR
24: M.p. 196 °C. [α]D = –86.7 (c = 0.97, CH2Cl2). 1H NMR
(400 MHz, CDCl3): δ = 0.4–1.4 (br. s, 3 H, BH3), 2.37 (s, 3 H,
3
H3C-Ph-SO2), 4.14 (ddd, J = 14.8, J = 11.4, JP,H = 2.4 Hz, 1 H,
3
SCH2), 4.24 (ddd, J = 14.8, JP,H = 8.6, J = 2.3 Hz, 1 H, SCH2),
(162 MHz, CDCl ): δ = 25.75 (br. s) ppm. IR (KBr): ν = 3866 (w),
˜
3
2
4.45 (ddd, JP,H = 16.1, J = 11.4, J = 2.3 Hz, 1 H, SCH2CH), 6.73
3466 (w), 3047 (m), 2927 (m), 2879 (w), 2842 (m), 2363 (s), 2341
(s), 1555 (w), 1492 (w), 1439 (m), 1387 (w), 1251 (s), 1201 (m), 1136
(s), 1072 (s), 920 (m), 862 (w), 819 (w) cm–1. MS (CI, isobutane):
m/z (%) = 534 (1) [M+ + 1], 533 (1), 530 (7), 300 (23), 299 (100),
298 (25), 289 (4), 233 (9), 232 (56). C33H33BNOPS (534.47): calcd.
C 74.30, H 6.24, N 2.63; found C 74.04, H 6.45, N 2.62.
(m, 2 H), 6.80 (t, J = 7.7 Hz, 2 H), 6.93 (m, 1 H), 7.13–7.24 (m, 8
H), 7.28–7.44 (m, 4 H), 7.64 (m, 5 H), 8.01 (m, 2 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 21.5 (CH3, H3C-Ph-SO2), 37.8 (d,
2
1JP,C = 28.3 Hz, CH, SCH2CH), 57.8 (d, JP, C = 9.2 Hz, CH2,
1
1
SCH2), 125.0 (d, JP, C = 51.8 Hz, 1 C, i-Ph), 126.2 (d, JP, C
=
55.0 Hz, 1 C, i-Ph), 126.3 (CH), 127.54 (CH), 127.57 (CH), 127.59
(CH), 128.1 (d, J = 10.1 Hz, CH), 128.8 (CH), 128.9 (CH), 129.3
(d, J = 9.8 Hz, CH), 129.5 (d, J = 4.2 Hz, CH), 130.6 (C), 131.2
(d, J = 2.4 Hz, CH), 132.2 (d, J = 2.3 Hz, CH), 132.3 (d, J =
9.0 Hz, CH), 133.0 (d, J = 8.6 Hz, CH), 133.4 (CH), 136.6 (C),
140.3 (C), 142.5 (C) ppm. 31P NMR (162 MHz, CDCl3): δ = 26.27
22: M.p. 94 °C. [α]D = +103.6 (c = 0.50, CHCl3). 1H NMR
(400 MHz, CDCl3): δ = 0.35–1.40 (br. s, 3 H, BH3), 3.60 (ddd, J =
3
14.8, J = 10.6, JP,H = 1.4 Hz, 1 H, SCH2), 4.00 (d, J = 14.9 Hz, 1
3
H, NCH2Ph), 4.06 (ddd, J = 14.8, JP,H = 11.6, J = 1.7 Hz, 1 H,
2
SCH2), 4.16 (d, J = 14.9 Hz, 1 H, NCH2Ph), 4.57 (ddd, JP,H
=
16.5, J = 10.6, J = 1.7 Hz, 1 H, SCH2CH), 6.88 (m, 2 H), 6.95 (m,
2 H), 7.05 (m, 1 H), 7.12–7.32 (m, 12 H), 7.40 (m, 1 H), 7.48 (m,
4 H), 7.56 (m, 1 H), 7.92 (m, 2 H) ppm. 13C NMR (100 MHz,
(br. s) ppm. IR (KBr): ν = 3924 (m), 3653 (w), 3463 (m), 3056 (m),
˜
2922 (w), 2410 (m), 1597 (w), 1493 (w), 1436 (m), 1398 (m), 1316
(s), 1239 (s), 1182 (w), 1154 (s), 1104 (s), 1067 (s), 1018 (w), 996
(w), 911 (m), 813 (m) cm–1. MS (CI, CH4): m/z (%) = 597 (2) [M+
+ 1], 596 (5) [M+ – 1], 299 (30), 187 (23), 173 (10), 172 (100), 155
(11), 133 (15), 111 (48), 109 (25), 105 (97), 91 (12), 88 (3), 87 (12).
1
CDCl3): δ = 38.7 (d, JP,C = 28.9 Hz, CH, SCH2CH), 46.4 (CH2,
2
1
NCH2Ph), 57.1 (d, JP,C = 8.2 Hz, CH2, SCH2), 125.6 (d, JP,C
=
1
51.7 Hz, 1 C, i-Ph), 126.2 (CH), 126.9 (d, JP,C = 54.6 Hz, 1 C, i-
Ph), 127.0 (CH), 127.2 (d, JP,C = 2.9 Hz, CH), 127.6 (d, JP,C
2.4 Hz, CH), 127.9 (CH), 128.0 (d, JP,C = 10.1 Hz, CH), 128.72
(CH), 128.76 (CH), 129.0 (d, JP,C = 9.6 Hz, CH), 129.8 (d, JP,C
=
23: M.p. 122 °C. [α]D = +162.35 (c = 0.85, CH2Cl2). 1H NMR
(300 MHz, CDCl3): δ = 0.4–1.4 (br. s, 3 H, BH3), 2.37 (s, 3 H,
=
3
H3C-Ph-SO2), 3.90 (ddd, J = 14.7, JP,H = 8.2, J = 2.1 Hz, 1 H,
4.3 Hz, CH), 131.0 (d, JP,C = 2.3 Hz, CH), 131.8 (d, JP,C = 2.3 Hz,
CH), 132.2 (C), 132.39 (d, JP,C = 8.9 Hz, CH), 132.44 (CH), 133.0
(d, JP,C = 8.5 Hz, CH), 138.3 (C), 141.1 (C) ppm. 31P NMR
3
SCH2), 4.33 (ddd, J = 14.7, J = 12.2, JP,H = 3.0 Hz, 1 H, SCH2),
2
4.58 (ddd, JP,H = 16.1, J = 12.2, J = 2.1 Hz, 1 H, SCH2CH), 6.84
(m, 4 H), 6.98 (m, 1 H), 7.13–7.27 (m, 8 H), 7.30 (m, 1 H), 7.44
(m, 1 H), 7.47–7.64 (m, 5 H), 7.76 (m, 2 H), 8.05 (m, 2 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 25.5 (CH3, H3C-Ph-SO2), 39.1
(162 MHz, CDCl ): δ = 26.38 (br. s) ppm. IR (KBr): ν = 3052 (m),
˜
3
2919 (m), 2847 (m), 2365 (s), 2344 (s), 1815 (w), 1582 (w), 1484
(m), 1439 (s), 1247 (s), 1117 (s), 1061 (s), 920 (m), 820 (w) cm–1.
MS (CI, isobutane): m/z (%) = 534 (20) [M+ + 1], 533 (10), 532
(19), 300 (20), 299 (100), 298 (24), 289 (12), 288 (11), 279 (4), 233
(10), 232 (69), 187 (11), 106 (15), 105 (10). C33H33BNOPS (534.47):
calcd. C 74.30, H 6.24, N 2.63; found C 74.27, H 6.08, N 2.50.
1
2
(d, JP,C = 28.0 Hz, CH, SCH2CH), 59.1 (d, JP,C = 9.8 Hz, CH2,
1
1
SCH2), 124.8 (d, JP, C = 51.7 Hz, 1 C, i-Ph), 126.0 (d, JP, C
=
50.5 Hz, 1 C, i-Ph), 126.3 (CH), 127.5 (d, JP,C = 2.6 Hz, CH), 127.6
(d, JP,C = 1.9 Hz, CH), 127.8 (CH), 128.1 (d, JP,C = 10.2 Hz, CH),
128.9 (CH), 129.0 (CH), 129.1 (d, JP,C = 9.8 Hz, CH), 129.8 (d,
(–)-Diphenyl{(1S)-1-phenyl-2-[(S)-N-(p-tolylsulfonyl)-S-phenylsulf- JP,C = 4.1 Hz, CH), 130.3 (C), 131.2 (d, JP,C = 2.0 Hz, CH), 132.1
onimidoyl]ethyl}phosphane–Borane (24) and (+)-Diphenyl{(1R)-1-
phenyl-2-[(S)-N-(p-tolylsulfonyl)-S-phenylsulfonimidoyl]ethyl}-
phosphane–Borane (23): According to method C, the phosphane–
(d, JP,C = 2.0 Hz, CH), 132.4 (d, JP,C = 8.9 Hz, CH), 133.3 (d, JP,C
= 8.7 Hz, CH), 133.6 (CH), 137.2 (C), 140.5 (C), 142.6 (C) ppm.
31P NMR (162 MHz, CDCl ): δ = 26.17 (br. s) ppm. IR (KBr): ν
˜
3
Eur. J. Org. Chem. 2010, 2157–2175
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2169

F. Lemasson, H.-J. Gais, J. Runsink, G. Raabe
FULL PAPER
= 3676 (w), 3652 (w), 3593 (w), 3447 (m), 3060 (m), 2924 (m), 2392 C(CH3)3], 3.38 (ddd, J = 14.7, J = 10.9, 3JP,H = 1.3 Hz, 1 H, SCH2),
3
(s), 1597 (w), 1493 (m), 1440 (m), 1399 (w), 1315 (s), 1226 (m),
3.92 (ddd, J = 14.7, JP,H = 11.7, J = 1.5 Hz, 1 H, SCH2), 4.49 (br.
2
1152 (s), 1091 (s), 1063 (s), 1021 (w), 997 (w), 911 (m), 816 (m) dd, JP,H = 16.7, J = 10.9 Hz, 1 H, SCH2CH), 6.72 (m, 2 H), 6.84
cm–1. MS (CI, CH4): m/z (%) = 596 (2) [M+ + 1], 299 (9), 291 (17), (t, J = 7.8 Hz, 2 H), 6.94 (m, 1 H), 7.04 (m, 2 H), 7.09–7.23 (m, 7
290 (10), 289 (34), 187 (31), 185 (10), 172 (61), 133 (15), 11 (30),
109 (30), 106 (8), 105 (100), 101 (16), 91 (13), 87 (26), 85 (10), 61
(21). Elemental analysis of a mixture of isomers 23 and 24:
H), 7.27 (m, 4 H), 7.34 (m, 1 H), 7.43 (m, 4 H), 7.53 (m, 3 H), 7.62
(m, 2 H), 7.89 (m, 2 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ =
1
19.3 [C, SiC(CH3)3], 27.1 [CH3, SiC(CH3)3], 38.1 (d, JP, C
=
C
33H33BNO3PS2 (597.17): calcd. C 66.33, H 5.57, N 2.34; found
28.8 Hz, CH, SCH2CH), 60.1 (d, 2JP,C = 6.5 Hz, CH2, SCH2), 126.0
1
C 66.34, H 5.45, N 2.23.
(d, JP,C = 51.6 Hz, 1 C, i-Ph), 126.99 (CH), 127.01 (CH), 127.15
(CH), 127.18 (CH), 127.21 (d, 1JP,C = 54.4 Hz, 1 C, i-Ph), 127.3 (d,
JP,C = 2.5 Hz, CH), 128.0 (d, JP,C = 10.1 Hz, CH), 128.1 (CH),
128.66 (CH), 128.74 (CH), 129.0 (d, JP,C = 9.7 Hz, CH), 129.6 (d,
JP,C = 4.4 Hz, CH), 130.9 (d, JP,C = 2.4 Hz, CH), 131.54 (CH),
131.56 (d, JP,C = 4.0 Hz, CH), 131.9 (C), 132.3 (d, JP,C = 8.8 Hz,
CH), 132.9 (d, JP,C = 8.4 Hz, CH), 135.26 (CH), 135.31 (CH), 135.7
(C), 135.8 (C), 143.0 (C) ppm. 31P NMR (162 MHz, CDCl3): δ =
(+)-Diphenyl{(S)-1-phenyl-2-[(S)-N(-tert-butyldiphenylsilyl)-S-
phenylsulfonimidoyl]ethyl}phosphane–Borane (26) and (–)-
Diphenyl{(R)-1-phenyl-2-[(S)-N-(tert-butyldiphenylsilyl)-S-
phenylsulfonimidoyl]ethyl}phosphane–Borane (25): According to
method C, the phosphane–boranes 25 and 26 were prepared start-
ing from the alkenyl sulfoximine 9 (2.0 g, 4.16 mmol), diphenyl-
phosphane (851 mg, 4.57 mmol) and tBuOK (46 mg, 410 µmol) in
THF (70 mL). After the complete conversion of sulfoximine 9,
BH3·THF (9.2 mL, 9.2 mmol) was added. Work-up after the mix-
ture was stirred for 1 h gave a mixture of 25 and 26 in a ratio of
58:42 [chiralpack-IA column, detector 254 nm, n-heptane/2-prop-
anol, 95:5, flow: 0.6 mL/min, 31 bar, Rt(25) = 12.31 min; Rt(26) =
19.53 min]. Purification by column chromatography (cyclohexane/
EtOAc, 93:7) afforded a mixture of 25 and 26 (2.27 g, 80%) as
sticky oil. The mixture was dissolved in hot n-heptane/2-propanol
(95:5). After a few days at room temperature, colorless crystals were
formed, which were collected and analyzed by HPLC. The ratio of
25 and 26 was 98.5:1.5. The crystals were once again dissolved in
hot n-heptane/2-propanol (95:5) and after a few days the crystals
were collected and analyzed. The phosphane–borane 25 (1.14 g,
40%, dr Ն 99:1) was obtained as colorless single crystals suitable
for X-ray crystal structure analysis. The first mother liquor (en-
riched in the minor isomer 26) was concentrated, and the residue
was dissolved in hot n-heptane/2-propanol (95:5). After two
crystallizations at 4 °C, the minor isomer 26 was isolated (920 mg,
32%, dr Ն 99:1) as colorless single crystals suitable for X-ray crys-
tal structure analysis.
26.05 (br. s) ppm. IR (KBr): ν = 3059 (m), 2929 (m), 2889 (m),
˜
2853 (m), 2385 (m), 2343 (m), 1969 (w), 1585 (w), 1483 (m), 1435
(m), 1320 (m), 1262 (m), 1149 (m), 1103 (m), 1060 (m), 999 (m),
906 (w), 819 (m), 771 (m), 732 (s), 695 (s), 598 (m), 526 (m), 491
(m) cm–1. MS (CI, isobutane): m/z (%) = 683 (5) [M+ + 2], 682 (15)
[M+ + 1], 681 (14) [M+], 680 (23), 380 (18), 300 (21), 299 (100),
298 (25). Elemental analysis of a mixture of isomers 25 and 26:
C42H45BNOPSSi (681.75): calcd. C 73.99, H 6.65, N 2.05; found
C 74.04, H 6.69, N 2.01.
(+)-Diphenyl{(1R,2R)-2-[(S)-N-methyl-S-phenylsulfonimidoyl]cyclo-
hexyl}phosphane–Borane (27) and (–)-Diphenyl{(1S,2S)-2-[(S)-N-
methyl-S-phenylsulfonimidoyl]cyclohexyl}phosphane–Borane (28):
According to method C, the phosphane–boranes 27 and 28 were
prepared starting from the alkenyl sulfoximine 17 (375 mg,
1.59 mmol), diphenylphosphane (330 mg, 1.77 mmol) and tBuOK
(18 mg, 590 µmol) in THF (12 mL). After complete conversion of
sulfoximine 17, BH3·THF (3.45 mL, 3.45 mmol) was added. Work-
up after the mixture was stirred for 1 h gave a mixture of 27 and 28
1
in a ratio of 1:1 (determined by H NMR). Purification by column
chromatography (cyclohexane/EtOAc, 85:15) afforded the phos-
phane–borane 27 (240 mg, 35%) as white crystalline solid and the
phosphane–borane 28 (315 mg, 46%) as white foam.
26: M.p. 135 °C. [α]D = +115.2 (c = 0.50, CHCl3). 1H NMR
(400 MHz, CDCl3): δ = 0.4–1.2 (br. s, 3 H, BH3), 0.99 [s, 9 H,
C(CH3)3], 3.38 (ddd, J = 14.6, 3JP,H = 10.3, J = 1.2 Hz, 1 H, SCH2),
4.03 (ddd, J = 14.6, J = 11.8, 3JP,H = 1.7 Hz, 1 H, SCH2), 4.43 (dd,
2JP,H = 16.5, J = 11.8, J = 1.2 Hz, 1 H, SCH2CH), 6.61 (m, 2 H),
6.76 (t, J = 7.7 Hz, 2 H), 6.90 (m, 1 H), 6.99 (t, J = 7.8 Hz, 2 H),
27: M.p. 72 °C. [α]D = +70.8 (c = 0.12, CHCl3). 1H NMR
(400 MHz, CDCl3): δ = 0.60–1.40 (br. s, 3 H, BH3), 1.50 (m, 2 H),
1.63 (m, 1 H), 1.77 (br. d, J = 15.0 Hz, 1 H), 1.90–2.24 (m, 4 H),
3
2.67 (s, 3 H, NCH3), 3.17 (br. dd, JP,H = 13.8, J = 5.8 Hz, 1 H,
2
7.11 (m, 4 H), 7.17–7.36 (m, 11 H), 7.39 (m, 1 H), 7.48 (m, 1 H), SCH), 4.57 (br. dd, JP,H = 19.6, J = 6.2 Hz, 1 H, SCHCHP), 7.49
7.63 (m, 2 H), 7.76 (4 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
(m, 11 H), 7.86 (m, 2 H), 8.14 (m, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 18.5 (CH2), 20.8 (CH2), 21.8 (CH2), 22.0 (d, J =
1.7 Hz, CH2), 26.0 (d, 1JP,C = 30.7 Hz, CH, SCHCHP), 29.6 (CH3,
1
19.4 [C, SiC(CH3)3], 27.1 [CH3, SiC(CH3)3], 39.2 (d, JP, C
=
28.7 Hz, CH, SCH2CH), 59.9 (d, 2JP,C = 6.8 Hz, CH2, SCH2), 125.8
1
1
2
1
(d, JP,C = 51.3 Hz, 1 C, i-Ph), 126.98 (d, JP,C = 54.6 Hz, 1 C, i-
Ph), 127.00 (d, JP,C = 3.0 Hz, CH), 127.1 (CH), 127.26 (CH),
127.28 (CH), 127.35 (CH), 127.90 (CH), 127.93 (d, JP,C = 9.9 Hz,
CH), 128.77 (CH), 128.82 (CH), 129.0 (d, JP,C = 9.6 Hz, CH), 129.6
NCH3), 58.5 (d, JP,C = 7.7 Hz, CH, SCH), 128.4 (d, JP, C
=
=
56.7 Hz, 1 C, i-Ph), 128.5 (d, JP,C = 9.8 Hz, CH), 128.70 (d, JP,C
10.0 Hz, 1 C), 128.72 (d, JP,C = 54.0 Hz, 1 C, i-Ph), 129.2 (CH),
129.7 (CH), 131.13 (CH), 131.17 (CH), 132.5 (CH), 132.6 (d, JP,C
1
(d, JP,C = 4.3 Hz, CH), 130.9 (d, JP,C = 2.4 Hz, CH), 131.3 (C), = 8.9 Hz, CH), 133.0 (d, JP,C = 8.6 Hz, CH), 136.8 (C, Si-Ph) ppm.
131.50 (CH), 131.55 (d, JP,C = 2.2 Hz, CH), 132.3 (d, JP,C = 8.8 Hz, 31P NMR (162 MHz, CDCl3): δ = 21.98 (br. s) ppm. IR (capillary,
CH), 132.8 (d, JP,C = 8.4 Hz, CH), 135.40 (CH), 135.44 (CH), dissolved in CHCl ): ν = 3881 (w), 3836 (w), 3674 (w), 3632 (w),
˜
3
135.82 (C),135.83 (C),142.7 (C) ppm. 31P NMR (162 MHz,
3450 (w), 3058 (w), 3012 (w), 2935 (m), 2871 (m), 2804 (w), 2391
CDCl ): δ = 25.42 (br. s) ppm. IR (KBr): ν = 3058 (m), 2929 (m), (s), 1560 (w), 1441 (m), 1247 (s), 1137 (s), 1105 (s), 1068 (s), 1002
˜
3
2889 (m), 2853 (m), 2385 (m), 2343 (m), 1585 (w), 1483 (m), 1435 (m), 868 (m), 832 (w) cm–1. MS (ESI–MS, MeOH): m/z (%) = 458
(m), 1320 (m), 1262 (m), 1149 (m), 1103 (m), 1060 (m), 999 (m), [M++23] (98), 434 [M+ – 1] (100). C25H31BNOPS (435.37): calcd.
906 (w), 819 (m) cm–1. MS (CI, isobutane): m/z (%) = 682 (15) [M+
+ 1], 681 (14) [M+], 680 (23) [M+ – 1], 380 (18), 300 (22), 299 (100),
298 (25), 289 (12).
C 68.97, H 7.18, N 3.22; found C 68.62, H 6.97, N 2.94.
28: M.p. 48 °C. [α]D = –15.9 (c = 1.90, CHCl3). 1H NMR
(400 MHz, CDCl3): δ = 0.60–1.70 (br. s, 3 H, BH3), 1.58 (m, 3 H),
1.96 (m, 2 H), 2.25 (m, 1 H), 2.34–2.53 (m, 2 H), 2.62 (s, 3 H,
25: M.p. 124 °C. [α]D = –86.6 (c = 0.50, CHCl3). 1H NMR
(400 MHz, CDCl3): δ = 0.4–1.2 (br. s, 3 H, BH3), 0.98 [s, 9 H, NCH3), 3.11 (br. dd, 3JP,H = 13.7, J = 5.4 Hz, 1 H, SCH), 3.53 (br.
2170
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 2157–2175

Asymmetric Allylic Alkylation
2
1
dd, JP,H = 19.1, J = 6.6 Hz, 1 H, SCHCHP), 7.26 (m, 2 H), 7.36–
2JP,C = 2.3 Hz, CH2, PCHCH2), 22.2 (CH2), 27.5 (d, JP, C
=
7.60 (m, 11 H), 7.74 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): 29.8 Hz, CH, SCHCHP), 47.0 (CH2), 59.3 (d, JP,C = 7.4 Hz, CH,
δ = 20.0 (CH2), 21.2 (CH2), 21.8 (CH2), 22.1 (CH2), 27.7 (d, JP,C
= 29.6 Hz, CH, SCHCHP), 29.7 (CH3, NCH3), 58.9 (d, JP,C
2
1
1
SCH), 126.1 (CH), 127.0 (CH), 127.65 (d, JP,C = 52.6 Hz, 1 C, i-
Ph), 127.74 (d, JP,C = 54.6 Hz, 1 C, i-Ph), 127.9 (CH), 128.6 (d,
JP,C = 9.9 Hz, CH), 128.7 (d, JP,C = 9.9 Hz, CH), 129.2 (CH), 129.5
(CH), 130.9 (d, JP,C = 3.1 Hz, CH), 131.2 (d, JP,C = 2.3 Hz, CH),
132.41 (d, JP,C = 8.4 Hz, CH), 132.42 (d, JP,C = 8.4 Hz, CH), 132.5
2
1
=
1
7.4 Hz, CH, SCH), 127.8 (d, JP,C = 54.3 Hz, 1 C, i-Ph), 127.9 (d,
1JP,C = 53.0 Hz, 1 C, i-Ph), 128.8 (d, JP,C = 9.6 Hz, CH), 128.9 (d,
JP,C = 9.8 Hz, CH), 129.5 (CH), 129.9 (CH), 131.1 (d, JP, C
=
1.8 Hz, CH), 131.5 (d, JP,C = 1.8 Hz, CH), 132.5 (d, JP,C = 8.1 Hz, (CH), 137.2 (C, Si-Ph), 141.4 (C, NCH2i-Ph) ppm. 31P NMR
CH), 132.63 (CH), 132.63 (d, JP,C = 7.8 Hz, CH), 136.8 (C, Si- (162 MHz, CDCl ): δ = 21.70 (br. s) ppm. IR (KBr): ν = 3944 (m),
˜
3
Ph) ppm. 31P NMR (162 MHz, CDCl3): δ = 21.53 (br. s) ppm. IR
(capillary, dissolved in CHCl ): ν = 3940 (w), 3882 (w), 3834 (w),
3930 (m), 3899 (m), 3696 (s), 3677 (s), 3612 (m), 3073 (m), 3052
(m), 2903 (m), 2871 (m), 2382 (s), 1619 (m), 1491 (w), 1438 (s),
˜
3
3783 (w), 3662 (w), 3534 (w), 3444 (m), 3160 (w), 3058 (w), 2935 1201 (m), 1126 (s), 1062 (s) cm–1. MS (CI, isobutane): m/z (%) =
(w), 2806 (w), 2393 (s), 2280 (w), 1590 (w), 1440 (s), 1301 (w), 1234
(s), 1138 (s), 1105 (s), 1070 (s), 862 (m) cm–1. MS (ESI–MS,
MeOH): m/z (%) = 460 (100), 458 [M++23] (90), 434 [M+ – 1]
(80). C25H31BNOPS (435.37): calcd. C 68.97, H 7.18, N 3.22; found
C 69.12, H 7.26, N 3.03.
511 (7) [M+], 510 (18) [M+ – 1], 280 (18), 279 (92), 278 (22), 267
(14), 233 (15), 232 (100), 106 (13). HRMS (ESI-TOF): calcd. for
C31H36BNOPS [M+ + H]: 512.2348; found 512.2349.
General Procedure for the Preparation of Phosphanyl Sulfoximines
(Method D): (–)-Diphenyl{(1R)-1-phenyl-2-[(S)-N-methyl-S-
phenylsulfonimidoyl]ethyl}phosphane (39): To a solution of the phos-
phane–borane 19 (100 mg, 218 µmol) in anhydrous and degassed
toluene (3 mL) contained in a round-bottom Schlenk flask was
added DABCO (26 mg, 228 µmol) at room temperature. The solu-
tion was heated at 40 °C for 2 h and the solvent was removed under
reduced pressure to give a sticky solid. A short chromatographic
column equipped with a Schlenk adaptor on the top and a 100 mL
round-bottom Schlenk flask at the bottom was filled with silica gel.
The column was kept under high vacuum for 5 min and filled with
argon. This was repeated 4 times. The silica gel was wetted with
Et2O/CH2Cl2 (97:3) by applying a low argon pressure on the top
of the column and low vacuum at the Schlenk flask. Then the sticky
solid was dissolved in a minimum amount of CH2Cl2, and the solu-
tion was loaded on the top of the column using a syringe. The
column was eluted with approximately 25 mL of Et2O/CH2Cl2
(97:3) using a syringe and collected in a Schlenk flask. The Schlenk
flask was disconnected from the column and the solvent was re-
moved under high vacuo, which gave phosphane 39 (93 mg, 96%)
as white solid; m.p. 146 °C. [α]D = –58.0 (c = 0.10, CH2Cl2). 1H
NMR (400 MHz, CDCl3): δ = 2.40 (s, 3 H, NCH3), 3.52 (ddd, J =
(+)-Diphenyl{(1R,2R)-2-[(S)-N-benzyl-S-phenylsulfonimidoyl]cyclo-
hexyl}phosphane–Borane (29) and (–)-Diphenyl{(1S,2S)-2-[(S)-N-
benzyl-S-phenylsulfonimidoyl]cyclohexyl}phosphane–Borane (30):
According to method C, the phosphane–boranes 29 and 30 were
prepared starting from the alkenyl sulfoximine 18 (1.14 g,
3.66 mmol), diphenylphosphane (718 mg, 3.86 mmol) and tBuOK
(40 mg, 356 µmol) in THF (40 mL). After the complete conversion
of sulfoximine 18, BH3·THF (8 mL, 8 mmol) was added. Work-up
after the mixture was stirred for 1 h gave a mixture of 29 and 30
1
in a ratio of 1:1 (determined by H NMR). Purification by column
chromatography (cyclohexane/EtOAc, 9:1) afforded the phos-
phane–borane 29 (768 mg, 41%) as white crystalline solid, and the
phosphane–borane 30 (730 mg, 39%) as white foam. The isomer
29 was crystallized from Et2O at –26 °C, which gave colorless single
crystals suitable for X-ray crystal structure analysis.
29: M.p. 124 °C. [α]D = +50.4 (c = 0.80, CH2Cl2). 1H NMR
(400 MHz, CDCl3): δ = 0.6–1.45 (br. s, 3 H, BH3) 1.45–1.68 (m, 3
3
H), 1.74 (m, 1 H), 1.92–2.32 (m, 4 H), 3.26 (dd, JP,H = 13.5, J =
5.5 Hz, 1 H, SCH), 3.91 (d, J = 14.3 Hz, 1 H), 4.30 (d, J = 14.3 Hz,
2
3
1 H), 4.70 (dd, JP,H = 19.5, J = 6.3 Hz, 1 H, SCHCHP), 7.27 (m,
14.8, JP,H = 7.5, J = 1.9 Hz, 1 H, SCH2), 3.77 (ddd, J = 14.8, J =
3
2
3 H), 7.34–7.50 (m, 10 H), 7.55 (m, 3 H), 7.83 (m, 2 H), 8.06 (m,
11.9, JP,H = 2.0 Hz, 1 H, SCH2), 4.04 (ddd, J = 11.9, JP,H = 3.3,
J = 1.9 Hz, 1 H, SCH2CH), 6.66 (m, 2 H), 6.76 (m, 3 H), 6.91 (m,
2 H), 7.00 (m, 2 H), 7.08 (m, 3 H), 7.22 (m, 1 H), 7.35 (m, 5 H),
7.55 (2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 28.2 (CH3,
NCH3), 38.4 (d, JP,C = 17.7 Hz, CH, SCH2CH), 57.0 (d, JP,C
24.1 Hz, SCH2), 125.1 (d, JP,C = 2.5 Hz, CH), 126.6 (d, JP, C
1.0 Hz, CH), 126.7 (d, JP,C = 6.7 Hz, CH), 127.45 (CH), 127.48
(CH), 127.7 (d, JP,C = 5.8 Hz, CH), 127.8 (d, JP,C = 4.9 Hz, CH),
127.9 (CH), 128.7 (CH), 130.8 (CH), 131.8 (d, 2JP,C = 18.2 Hz, CH,
2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 19.5 (CH2), 20.9
2
(CH2), 21.9 (CH2), 22.1 (d, JP,C = 1.7 Hz, CH2, PCHCH2), 26.3
(d, 1JP,C = 30.5 Hz, CH, SCHCHP), 47.1 (CH2, NCH2Ph), 58.7 (d,
2JP,C = 7.7 Hz, CH, SCH), 126.3 (CH), 127.4 (CH), 128.0 (CH),
1
2
=
=
1
128.3 (d, JP,C = 51.9 Hz, 1 C, i-Ph), 128.5 (d, JP,C = 9.7 Hz, CH),
1
128.60 (d, JP,C = 54.2 Hz, 1 C, i-Ph), 128.66 (d, JP,C = 9.9 Hz,
CH), 129.1 (CH), 129.5 (CH), 131.0 (d, JP,C = 2.0 Hz, CH), 131.1
(d, JP,C = 2.1 Hz, CH), 132.46 (d, JP,C = 9.0 Hz, CH), 132.53 (CH),
132.9 (d, JP,C = 8.7 Hz, CH), 137.2 (C, Si-Ph), 141.7 (C, NCH2i-
Ph) ppm. 31P NMR (162 MHz, CDCl3): δ = 21.61 (br. s) ppm. IR
2
1
Po-Ph), 132.98 (d, JP,C = 21.0 Hz, CH, Po-Ph), 132.99 (d, JP,C
=
1
11.2 Hz, 1 C, i-Ph), 134.0 (d, JP,C = 15.6 Hz, 1 C, i-Ph), 135.8 (d,
2JP, C = 8.1 Hz, 1 C, PCHi-Ph), 136.1 (C) ppm. 31P NMR
(162 MHz, CDCl3): δ = 1.47 (s) ppm.
(KBr): ν = 3794 (w), 3685 (w), 3434 (m), 3051 (m), 2931 (m), 2855
˜
(m), 2344 (w), 1611 (m), 1438 (s), 1258 (s), 1203 (m), 1123 (m),
1061 (m), 1001 (w), 880 (m), 832 (m) cm–1. MS (CI, CH4): m/z
(%) = 510 (2) [M+ – 1], 280 (18), 279 (100), 278 (25), 232 (86).
C31H35BNOPS (511.47): calcd. C 72.80, H 6.90, N 2.74; found
C 72.60, H 6.99, N 2.62.
(+)-Diphenyl{(1S)-1-phenyl-2-[(S)-N-methyl-S-phenylsulfonimidoyl]-
ethyl}phosphane (40): According to method D, phosphane 40 was
prepared from the phosphane–borane 20 (100 mg, 218 µmol) and
DABCO (26 mg, 228 µmol) in toluene (3 mL) at 40 °C for 2 h. Pu-
rification by column chromatography afforded phosphane 40
30: M.p. 59–61 °C. [α]D = –14.5 (c = 1.03, CHCl3). 1H NMR
(400 MHz, CDCl3): δ = 0.6–1.51 (br. s, 3 H, BH3), 1.51–1.71 (m, 3 (93 mg, 94%) as white solid; m.p. 111–113 °C. [α]D = +120.7 (c =
H), 1.94 (m, 1 H), 2.09 (m, 1 H), 2.27 (m, 1 H), 2.37–2.58 (m, 2 0.14, CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 2.58 (s, 3 H,
3
2
3
H), 3.15 (dd, JP,H = 13.7, J = 5.2 Hz, 1 H, SCH), 3.70 (dd, JP,H
= 19.0, J = 6.3 Hz, 1 H, SCHCHP), 3.96 (d, J = 14.8 Hz, 1 H,
NCH2), 4.24 (d, J = 14.8 Hz, 1 H, NCH2), 7.19 (m, 1 H), 7.28 (m,
NCH3), 3.48 (ddd, J = 14.5, JP,H = 7.6, J = 1.4 Hz, 1 H, SCH2),
3
3.78 (ddd, J = 14.5, J = 12.0, JP,H = 2.3 Hz, 1 H, SCH2), 3.90
(ddd, J = 12.0, JP,H = 2.9, J = 1.4 Hz, 1 H, SCH2CH), 6.91 (m, 4
2
4 H), 7.33–7.50 (m, 8 H), 7.53–7.64 (m, 5 H), 7.77 (m, 2 H) ppm. H), 7.05 (m, 5 H), 7.15 (m, 1 H), 7.29–7.44 (m, 7 H), 7.46–7.55 (m,
13C NMR (100 MHz, CDCl3): δ = 19.9 (CH2), 21.1 (CH2), 21.9 (d, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 29.4 (CH3, NCH3),
Eur. J. Org. Chem. 2010, 2157–2175
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2171

F. Lemasson, H.-J. Gais, J. Runsink, G. Raabe
FULL PAPER
1
2
2
39.9 (d, JP,C = 18.6 Hz, CH, SCH2CH), 58.3 (d, JP,C = 23.5 Hz, SCH2), 4.02 (dt, J = 12.3, JP,H = 2.2 Hz, 1 H, SCH2CH), 4.17
3
CH2, SCH2), 126.4 (d, J = 2.5 Hz, CH), 127.7 (d, J = 6.5 Hz, CH),
127.9 (d, J = 1.2 Hz, CH), 128.4 (CH), 128.6 (d, J = 7.6 Hz, CH),
(ddd, J = 14.4, J = 12.3, JP,H = 2.7 Hz, 1 H, SCH2), 6.82 (m, 2
H), 6.90 (m, 2 H), 6.97 (m, 3 H), 7.06 (m, 2 H), 7.17 (m, 3 H),
128.8 (CH), 128.9 (CH), 129.2 (CH), 129.6 (CH), 132.2 (CH), 132.7 7.31–7.48 (m, 5 H), 7.53 (m, 3 H), 7.60 (m, 2 H), 7.74 (m, 2 H)
2
1
(d, JP,C = 17.9 Hz, CH, Po-Ph), 133.94 (d, JP,C = 17.1 Hz, 1 C, i- ppm. 13C NMR (100 MHz, CDCl3): δ = 21.4 (CH3, SO2-pCH3Ph),
2
1
1
2
Ph), 134.03 (d, JP,C = 21.1 Hz, CH, Po-Ph), 135.0 (d, JP, C
=
40.0 (d, JP,C = 20.2 Hz, CH, SCH2CH), 60.7 (d, JP,C = 25.9 Hz,
CH2, SCH2), 126.4 (CH), 126.7 (d, JP,C = 2.4 Hz, CH), 127.8 (d,
JP,C = 6.6 Hz, CH), 127.99 (CH), 128.03 (CH), 128.66 (CH), 128.76
(CH), 128.77 (CH), 128.84 (CH), 128.9 (CH), 130.0 (CH), 132.7
2
16.4 Hz, 1 C, i-Ph), 137.3 (d, JP,C = 7.8 Hz, 1 C, PCHi-Ph), 137.8
(C) ppm. 31P NMR (162 MHz, CDCl3): δ = 2.30 (s) ppm.
(–)-Diphenyl{(1R)-1-phenyl-2-[(S)-N-benzyl-S-phenylsulfonimidoyl]-
ethyl}phosphane (41): According to method D, phosphane 41 was
prepared from the phosphane–borane 21 (178 mg, 333 µmol) and
DABCO (41 mg, 365 µmol) in toluene (5 mL) at 40 °C for 2 h. Pu-
rification by column chromatography afforded phosphane 41
(169 mg, 98%) as white solid; m.p. 157–158 °C. [α]D = –92.2 (c =
2
1
(d, JP,C = 18.2 Hz, CH, Po-Ph), 133.1 (d, JP,C = 16.8 Hz, 1 C, i-
Ph), 133.6 (CH), 134.20 (d, 2JP,C = 21.7 Hz, CH, Po-Ph), 134.23 (d,
2
1JP,C = 15.7 Hz, 1 C, i-Ph), 135.6 (d, JP,C = 7.8 Hz, 1 C, PCHi-
Ph), 137.1 (C), 140.6 (C), 142.3 (C) ppm. 31P NMR (162 MHz,
CDCl3): δ = 3.39 (s) ppm.
0.40, CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 3.67 (ddd, J = (–)-Diphenyl{(R)-1-phenyl-2-[(S)-N-(tert-butyldiphenylsilyl)-S-phen-
14.7, JP,H = 7.6, J = 1.6 Hz, 1 H, SCH2), 3.87 (d, J = 14.7 Hz, 1
H, NCH2Ph), 3.90 (ddd, J = 14.7, J = 12.0, JP,H = 2.0 Hz, 1 H,
3
ylsulfonimidoyl]ethyl}phosphane (44): According to method D,
phosphane 44 was prepared starting from the phosphane–borane
3
SCH2), 4.01 (d, J = 14.7 Hz, 1 H, NCH2Ph), 3.67 (ddd, J = 12.0, 25 (80 mg, 117 µmol) and DABCO (15 mg, 134 µmol) in toluene
2JP,H = 4.6, J = 1.6 Hz, 1 H, SCH2CH), 6.76 (m, 2 H), 6.87 (m, 3
(2.5 mL) at 40 °C for 2 h. Purification by column chromatography
H), 6.96 (m, 2 H), 7.06 (m, 2 H), 7.11–7.26 (m, 8 H), 7.32 (m, 1 afforded phosphane 44 (72 mg, 92%) as sticky syrup. [α]D = –61.3
H), 7.43 (m, 3 H), 7.48 (m, 2 H), 7.63 (m, 2 H) ppm. 13C NMR (c = 0.16, CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 0.99 [s, 9 H,
1
(100 MHz, CDCl3): δ = 39.4 (d, JP,C = 17.9 Hz, CH, SCH2CH), C(CH3)3], 3.38 (ddd, J = 14.4, 3JP,H = 8.4, J = 1.1 Hz, 1 H, SCH2),
46.2 (CH2, NCH2Ph), 58.4 (d, 2JP,C = 24.0 Hz, CH2, SCH2), 126.10 3.67 (m, 1 H, SCH2), 3.17 (m, 1 H, SCH2CH), 6.66 (m, 2 H), 6.88
(CH), 126.12 (CH), 127.2 (CH), 127.69 (CH), 127.71 (d, JP,C
6.9 Hz, CH), 127.9 (CH), 128.4 (CH), 128.5 (CH), 128.7 (d, JP,C
=
=
(m, 5 H), 7.04 (m, 4 H), 7.11–7.29 (m, 7 H), 7.30–7.45 (m, 6 H),
7.50–7.62 (m, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 19.3
1
7.6 Hz, CH), 128.8 (d, JP,C = 6.6 Hz, CH), 128.9 (CH), 129.7 (CH), [C, C(CH3)3], 27.1 [CH3, C(CH3)3], 39.6 (d, JP,C = 18.1 Hz, CH,
132.0 (CH), 132.8 (d, 2JP,C = 18.1 Hz, CH, Po-Ph), 133.99 (d, 1JP,C
= 17.7 Hz, 1 C, i-Ph), 134.01 (d, 2JP,C = 20.9 Hz, CH, Po-Ph), 135.1
SCH2CH), 62.3 (d, JP,C = 21.1 Hz, CH2, SCH2), 126.0 (d, JP,C
=
2
2.5 Hz, CH), 126.9 (CH), 127.0 (CH), 127.2 (CH), 127.6 (CH),
(d, 1JP,C = 16.0 Hz, 1 C, i-Ph), 137.0 (d, 2JP,C = 7.9 Hz, 1 C, PCHi- 127.7 (d, JP,C = 6.6 Hz, CH), 128.0 (CH), 128.4 (CH), 128.5 (CH),
Ph), 137.8 (C), 141.2 (C) ppm. 31P NMR (162 MHz, CDCl3): δ = 128.59 (CH), 128.65 (d, JP,C = 2.9 Hz, CH), 129.4 (CH), 131.3
2
2
1.67 (s) ppm.
(CH), 132.8 (d, JP,C = 18.1 Hz, CH, Po-Ph), 133.9 (d, JP, C =
1
20.5 Hz, CH, Po-Ph), 134.1 (d, JP,C = 9.2 Hz, 1 C, i-Ph), 135.2 (d,
1JP,C = 16.0 Hz, 1 C, i-Ph), 135.34 (CH), 135.37 (CH), 135.5 (C),
136.0 (C), 136.1 (C), 137.2 (d, 2JP,C = 8.1 Hz, 1 C, PCHi-Ph), 143.4
(C) ppm. 31P NMR (162 MHz, CDCl3): δ = 2.26 (s) ppm.
(+)-Diphenyl{(1S)-1-phenyl-2-[(S)-N-benzyl-S-phenylsulfonimidoyl]-
ethyl}phosphane (42): According to method D, phosphane 42 was
prepared from the phosphane–borane 22 (100 mg, 188 µmol) and
DABCO (23 mg, 205 µmol) in toluene (3 mL) at 40 °C for 2 h. Pu-
rification by column chromatography afforded phosphane 42
(92 mg, 94%) as white solid; m.p. 129 °C. [α]D = +117.27 (c = 0.11,
(+)-Diphenyl{(S)-1-phenyl-2-[(S)-N-(tert-butyldiphenylsilyl)-S-phen-
ylsulfonimidoyl]ethyl}phosphane (45): According to method D,
CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 3.47 (ddd, J = 14.6, phosphane 45 was prepared starting from the phosphane–borane
3JP,H = 7.8, J = 1.4 Hz, 1 H, SCH2), 3.78 (ddd, J = 14.6, J = 12.0,
3JP,H = 1.9 Hz, 1 H, SCH2), 3.87 (d, J = 14.8 Hz, 1 H, NCH2Ph),
26 (118 mg, 173 µmol) and DABCO (21 mg, 187 µmol) in toluene
(3 mL) at 40 °C for 2 h. Purification by column chromatography
4.01 (br. d, J = 12.0 Hz, 1 H, SCH2CH), 4.07 (d, J = 14.8 Hz, 1 afforded phosphane 45 (107 mg, 93%) as white foam; m.p. 76 °C.
1
H, NCH2Ph), 6.80–6.90 (m, 4 H), 6.92–7.02 (m, 5 H), 7.05–7.15
(m, 2 H), 7.19 (m, 4 H), 7.25 (m, 4 H), 7.32 (m, 1 H), 7.39 (m, 3
H), 7.50 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 38.8 (d,
[α]D = +109.0 (c = 0.1, CH2Cl2). H NMR (400 MHz, CDCl3): δ
3
= 1.04 [s, 9 H, C(CH3)3], 3.39 (ddd, J = 14.4, JP,H = 7.6, J =
1.3 Hz, 1 H, SCH2), 3.76 (ddd, J = 14.4, J = 12.1, JP,H = 2.1 Hz,
3
1JP,C = 18.6 Hz, CH, SCH2CH), 45.5 (CH2, NCH2Ph), 57.7 (d, 1 H, SCH2), 4.09 (m, 1 H, SCH2CH), 6.60 (m, 2 H), 6.81 (m, 2
2JP,C = 23.0 Hz, CH, SCH2), 125.1 (CH), 125.3 (d, JP,C = 2.6 Hz, H), 6.89 (m, 3 H), 7.04 (m, 4 H), 7.15 (m, 1 H), 7.18–7.46 (m, 14
CH), 126.0 (CH), 126.7 (d, JP,C = 6.5 Hz, CH), 126.84 (CH), 126.85
H), 7.64 (m, 2 H), 7.74 (m, 2 H) ppm. 13C NMR (100 MHz,
1
(CH), 127.4 (CH), 127.6 (d, JP,C = 7.4 Hz, CH), 127.7 (CH), 127.8 CDCl3): δ = 19.4 [C, C(CH3)3], 27.2 [CH3, C(CH3)3], 40.6 (d, JP,C
(d, JP,C = 6.4 Hz, CH), 128.0 (CH), 128.6 (CH), 131.2 (CH), 131.7 = 18.3 Hz, CH, SCH2CH), 62.0 (d, JP,C = 21.5 Hz, CH2, SCH2),
(d, JP,C = 17.9 Hz, CH, Po-Ph), 132.94 (d, JP,C = 17.3 Hz, 1 C, i- 126.0 (d, JP,C = 2.5 Hz, CH), 127.0 (CH), 127.2 (CH), 127.5 (CH),
2
2
1
2
1
Ph), 133.02 (d, JP,C = 21.0 Hz, CH, Po-Ph), 134.0 (d, JP, C
=
127.6 (CH), 127.7 (d, JP,C = 6.7 Hz, CH), 127.8 (CH), 128.4 (CH),
128.5 (CH), 128.60 (CH), 128.62 (CH), 128.67 (d, JP,C = 2.2 Hz,
CH), 129.4 (CH), 131.3 (CH), 132.9 (d, JP,C = 18.3 Hz, CH, Po-
Ph), 133.9 (d, JP,C = 20.8 Hz, CH, Po-Ph), 134.2 (d, JP, C
17.2 Hz, 1 C, i-Ph), 135.2 (d, JP,C = 16.1 Hz, 1 C, i-Ph), 135.43
16.4 Hz, 1 C, i-Ph), 136.3 (d, JP,C = 7.9 Hz, 1 C, PCHi-Ph), 137.6
(C), 140.3 (C) ppm. 31P NMR (162 MHz, CDCl3): δ = 2.42 (s)
ppm.
2
2
1
=
1
(+)-Diphenyl{(1R)-1-phenyl-2-[(S)-N-(p-tolylsulfonyl)-S-phenyl-
sulfonimidoyl]ethyl}phosphane (43): According to method D, phos-
phane 43 was prepared from the phosphane–borane 23 (46 mg,
77 µmol) and DABCO (11 mg, 98 µmol) in toluene (5 mL) at 40 °C
for 2 h. Purification by column chromatography afforded phos-
phane 43 (42 mg, 94%) as white solid; m.p. 145 °C. [α]D = +56.0 (c
2
(CH), 135.46 (CH), 136.0 (C), 136.1 (C), 136.6 (d, JP,C = 7.9 Hz,
1 C, PCHi-Ph), 142.9 (C) ppm. 31P NMR (162 MHz, CDCl3): δ =
2.43 (s) ppm.
(+)-Diphenyl{(1R,2R)-2-[(S)-N-methyl-S-phenylsulfonimidoyl]cyclo-
hexyl}phosphane (35): According to method D, phosphane 35 was
= 0.1, CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 2.35 (s, 3 H, prepared starting from the phosphane–borane 27 (112 mg,
3
SO2-pCH3Ph), 3.77 (ddd, J = 14.4, JP,H = 6.1, J = 2.0 Hz, 1 H, 258 µmol) and DABCO (32 mg, 285 µmol) in toluene (3 mL) at
2172
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 2157–2175

Asymmetric Allylic Alkylation
40 °C for 1 h. Purification by column chromatography afforded
153 µmol) and DABCO (18 mg, 160 µmol) in toluene (2.5 mL) at
40 °C for 1 h. Purification by column chromatography afforded
phosphane 35 (105 mg, 97%) as white solid; m.p. 122 °C. [α]D
+207.0 (c = 0.10, CH2Cl2). H NMR (400 MHz, CDCl3): δ = 1.37 phosphane 38 (71 mg, 93%) as white solid; m.p. 89 °C. [α]D = –34.0
=
1
1
(br. d, J = 14.3 Hz, 1 H), 1.56 (br. d, J = 10.3 Hz, 2 H), 1.81–2.36
(m, 5 H), 2.68 (s, 3 H, NCH3), 3.04 (br. t, J = 6.5 Hz, 1 H, SCH),
(c = 0.10, CH2Cl2). H NMR (400 MHz, CDCl3): δ = 1.40 (m, 1
H), 1.57–1.73 (m, 2 H), 1.93 (m, 1 H), 2.15 (m, 2 H), 2.58 (m, 1
3.94 (br. s, 1 H, SCHCHP), 7.31 (m, 6 H), 7.49 (m, 5 H), 6.65 (m, H), 2.76 (m, 1 H), 2.98 (m, 1 H, SCH), 3.13 (br. s, 1 H, SCHCHP),
4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.0 (CH2), 21.2 (d, 3.91 (d, J = 14.8 Hz, 1 H, NCH2Ph), 4.23 (d, J = 14.8 Hz, 1 H,
JP,C = 8.2 Hz, CH2), 21.8 (d, JP,C = 5.1 Hz, CH2), 22.7 (d, JP,C
=
NCH2Ph), 7.09 (m, 4 H), 7.17 (m, 1 H), 7.20–7.49 (m, 12 H), 7.56–
1
11.2 Hz, CH2), 29.7 (CH3, NCH3), 30.4 (d, JP,C = 14.0 Hz, CH, 7.65 (m, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 20.3 (d, JP,C
2
SCHCHP), 60.4 (d, JP,C = 17.6 Hz, CH, SCH), 128.2 (d, JP,C
=
= 7.6 Hz, CH2), 20.5 (CH2), 20.8 (d, JP,C = 4.8 Hz, CH2), 21.3 (d,
1
7.7 Hz, CH), 128.4 (d, JP,C = 7.5 Hz, CH), 128.8 (CH), 128.96 JP,C = 11.8 Hz, CH2), 30.1 (d, JP,C = 15.5 Hz, CH, SCHCHP),
2
(CH), 128.97 (CH), 129.6 (CH), 132.1 (CH), 133.5 (d, JP, C
=
=
46.0 (CH2, NCH2Ph), 59.4 (d, JP,C = 17.1 Hz, CH, SCH), 125.0
(CH), 126.1 (CH), 126.8 (CH), 127.3 (d, JP,C = 7.7 Hz, CH), 127.4
(d, JP,C = 7.8 Hz, CH), 127.45 (d, JP,C = 7.5 Hz, CH), 127.93 (CH),
1
15.1 Hz, CH), 133.7 (d, JP,C = 15.2 Hz, CH), 136.2 (d, JP, C
1
44.6 Hz, 1 C, i-Ph), 136.3 (d, JP,C = 46.4 Hz, 1 C, i-Ph), 137.5 (C,
Si-Ph) ppm. 31P NMR (162 MHz, CDCl3): δ = –12.79 (s) ppm.
127.98 (CH), 128.05 (CH), 128.7 (CH), 131.2 (CH), 132.2 (d, JP,C
1
= 10.6 Hz, CH), 132.4 (d, JP,C = 11.5 Hz, CH), 134.4 (d, JP,C
=
(–)-Diphenyl{(1S,2S)-2-[(S)-N-methyl-S-phenylsulfonimidoyl]cyclo-
hexyl}phosphane (36): According to method D, phosphane 36 was
prepared starting from the phosphane–borane 28 (71 mg,
163 µmol) and DABCO (20 mg, 178 µmol) in toluene (2.5 mL) at
40 °C for 1 h. Purification by column chromatography afforded
phosphane 36 (63 mg, 91%) as sticky syrup. [α]D = –11.4 (c = 0.22,
CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 1.40 (m, 1 H), 1.64 (m,
2 H), 1.91 (m, 1 H), 1.99–2.22 (m, 2 H), 2.55 (m, 1 H), 2.60 (s, 3
H, NCH3), 2.70 (br. d, J = 14.2 Hz, 1 H), 2.91 (br. t, J = 6.1 Hz,
1 H, SCH), 2.99 (br. s, 1 H, SCHCHP), 7.01 (m, 2 H), 7.09 (m, 2
H), 7.23 (m, 1 H), 7.29 (m, 3 H), 7.36 (m, 2 H), 7.43 (m, 2 H), 7.58
1
33.1 Hz, 1 C, i-Ph), 134.6 (d, JP,C = 33.1 Hz, 1 C, i-Ph), 136.8 (C,
Si-Ph), 140.7 (C, NCH2i-Ph) ppm. 31P NMR (162 MHz, CDCl3):
δ = –13.48 (s) ppm.
General Procedure for the Allylic Alkylation (Method E). (+)-Di-
methyl 2-[(R,E)-1,3-Diphenylallyl]malonate [(R)-47]: In a round-
bottom Schlenk flask, Pd2(dba)3·CHCl3 (7.4 mg, 7 µmol) and
phosphane 37 (7.1 mg, 14 µmol) were dissolved in anhydrous and
degassed CH2Cl2 (2 mL). Then the mixture was heated at reflux
for 1 h. After the mixture was warmed to room temperature, it was
transferred to a Schlenk flask containing acetate rac-46 (120 mg,
480 µmol). The volume of the mixture was adjusted to 3 mL
through addition of CH2Cl2 and the mixture was treated sub-
sequently with dimethyl malonate (138 µL, 1.19 mmol), N,O-bis-
(trimethylsilyl)acetamide (320 µL, 1.19 mmol) and lithium acetate
(1 mg). After the mixture was stirred for 50 min (complete conver-
sion of acetate rac-46 by TLC), it was quenched with water (3 mL)
and extracted with EtOAc (3ϫ3 mL). The combined organic
phases were dried (MgSO4) and concentrated in vacuo. Purification
by column chromatography (cyclohexane/EtOAc, 9:1) gave malon-
ate (R)-47 (151 mg, 98%) with 97% ee {HPLC: chiralcel-OD-H
column, detector 254 nm, n-heptane/2-propanol, 95:5, flow:
(m, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.3 (d, JP,C
=
7.8 Hz, CH2), 21.61 (d, JP,C = 3.4 Hz, CH2), 21.63 (CH2), 22.2 (d,
2
JP,C = 12.0 Hz, CH2), 29.7 (CH3, NCH3), 31.3 (d, JP,C = 15.6 Hz,
CH, SCHCHP), 60.0 (d, 1JP,C = 16.9 Hz, CH, SCH), 128.3 (d, JP,C
= 7.6 Hz, CH), 128.4 (d, JP,C = 7.9 Hz, CH), 128.9 (CH), 129.0
(CH), 129.1 (CH), 129.8 (CH), 132.1 (CH), 133.2 (d, JP, C
=
=
1
17.0 Hz, CH), 133.4 (d, JP,C = 17.6 Hz, CH), 135.4 (d, JP, C
1
15.1 Hz, 1 C, i-Ph), 135.5 (d, JP,C = 14.8 Hz, 1 C, i-Ph), 136.9 (C,
Si-Ph) ppm. 31P NMR (162 MHz, CDCl3): δ = –13.67 (s) ppm.
(+)-Diphenyl{(1R,2R)-2-[(S)-N-benzyl-S-phenylsulfonimidoyl]cyclo-
hexyl}phosphane (37): According to method D, phosphane 37 was
prepared starting from phosphane–borane 29 (200 mg, 391 µmol)
and DABCO (48 mg, 428 µmol) in toluene (6 mL) at 40 °C for 1 h.
Purification by column chromatography afforded phosphane 37
(189 mg, 97%) as white solid; m.p. 129 °C. [α]D = +78.0 (c = 0.10,
CH2Cl2). 1H NMR (400 MHz, CDCl3): δ = 1.38 (m, 1 H), 1.58 (m,
2 H), 1.80 (br. d, J = 14.9 Hz, 1 H), 1.93 (m, 1 H), 2.06 (m, 1 H),
2.18 (m, 1 H), 2.38 (m, 1 H), 3.15 (m, 1 H, SCH), 3.97 (d, J =
15.0 Hz, 1 H, NCH2Ph), 4.14 (br. s, 1 H, SCHCHP), 4.32 (d, J =
15.0 Hz, 1 H, NCH2Ph), 7.23–7.38 (m, 9 H), 7.43 (m, 4 H), 7.51
(m, 3 H), 7.64 (m, 2 H), 7.72 (m, 2 H) ppm. 13C NMR (100 MHz,
0.75 mL/min, 40 bar, Rt[(R)-47]
= 15.28 min; Rt[(S)-47] =
19.53 min} as colorless viscous oil, which solidified upon standing.
(+)-(R)-(E)-Dimethyl 2-(Pent-3-en-2-yl)malonate [(R)-49]: Accord-
ing to method E, malonate (R)-49 was prepared starting from ace-
tate rac-48 (61 mg, 480 µmol), phosphane 37 (7.1 mg, 14 µmol),
Pd2(dba)3·CHCl3 (7.4 mg, 7 µmol), dimethyl malonate (138 µL,
1.19 mmol), N,O-bis(trimethylsilyl)acetamide (320 µL, 1.19 mmol)
and lithium acetate (1 mg). After the mixture was stirred for 3.5 h
(complete conversion of acetate rac-48 according to TLC), it was
quenched and submitted to work-up. Purification by column
chromatography (n-pentane/Et2O, 8:1) gave malonate (R)-49
(90 mg, 95%) with 59% ee {GC: β-cyclodextrin CP column, Rt[(S)-
49] = 32.82 min; Rt[(R)-49] = 32.92 min} as colorless viscous oil.
CDCl3): δ = 19.8 (CH2), 20.1 (d, JP,C = 8.0 Hz, CH2), 20.8 (d, JP,C
1
= 5.0 Hz, CH2), 21.7 (d, JP,C = 11.0 Hz, CH2), 29.4 (d, JP,C
=
=
2
13.8 Hz, CH, SCHCHP), 46.0 (CH2, NCH2Ph), 59.4 (d, JP,C
18.0 Hz, CH, SCH), 125.0 (CH), 126.0 (CH), 126.8 (CH), 127.3 (d,
JP,C = 7.7 Hz, CH), 127.4 (d, JP,C = 7.4 Hz, CH), 127.92 (CH),
(+)-(R)-Dimethyl 2-(Cyclohex-2-enyl)malonate [(R)-51]: According
to method E, malonate (R)-51 was prepared starting from acetate
rac-50 (61 mg, 480 µmol), phosphane 37 (7.1 mg, 14 µmol),
Pd2DBA3·CHCl3 (7.4 mg, 7 µmol), dimethyl malonate (138 µL,
1.19 mmol), N,O-bis(trimethylsilyl)acetamide (320 µL, 1.19 mmol)
and lithium acetate (1 mg). After the mixture was stirred for 24 h
(complete conversion according to TLC), it was quenched and sub-
mitted to work-up. Purification by column chromatography (n-pen-
tane/Et2O, 10:1) gave malonate (R)-51 (71 mg, 70%) with 36% ee
{GC: β-cyclodextrin CP column, Rt[(S)-51] = 25.30 min; Rt[(R)-51]
= 25.48 min} as colorless viscous oil.
127.97 (CH), 128.04 (CH), 128.7 (CH), 131.1 (CH), 132.2 (d, JP,C
1
= 10.6 Hz, CH), 132.4 (d, JP,C = 11.2 Hz, CH), 135.1 (d, JP,C
=
1
30.7 Hz, 1 C, i-Ph), 135.3 (d, JP,C = 32.1 Hz, 1 C, i-Ph), 136.6 (C,
Si-Ph), 141.0 (C, NCH2i-Ph) ppm. 31P NMR (162 MHz, CDCl3):
δ = –13.09 (s) ppm. MS (CI, isobutane): m/z (%) = 498 (4) [M+ + 1],
391 (6), 268 (20), 267 (100), 266 (7). HRMS (ESI-TOF): calcd. for
C31H34NOPS [M+ + H]: 498.2015; found 498.2009.
(–)-Diphenyl{(1S,2S)-2-[(S)-N-benzyl-S-phenylsulfonimidoyl]cyclo-
hexyl}phosphane (38): According to method D, phosphane 38 was
prepared starting from the phosphane–borane 30 (78 mg,
Eur. J. Org. Chem. 2010, 2157–2175
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2173

F. Lemasson, H.-J. Gais, J. Runsink, G. Raabe
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Acknowledgments
Financial support of this work by the Deutsche Forschungsgemein-
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We thank Dr. C. Lehmann, MPI Mülheim, for collecting the data
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Received: December 14, 2009
Published Online: February 23, 2010
Eur. J. Org. Chem. 2010, 2157–2175
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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