Anionic cross-coupling reaction of α-metallated alkenyl sulfoximines and alkenyl sulfoximines with cuprates featuring a 1,2-metal-ate rearrangement of sulfoximine-substituted higher order alkenyl cuprates and an α-metallation of alkenyl sulfoximines by cuprates

Article abstract of DOI:10.1002/chem.200800455

(E)- and (Z)-configured αlithioalkenyl sulfoximines, which are available through lithiation of the corresponding alkenyl sulfoximines, undergo a anionic cross-coupling reaction (ACCR) with organocuprates with formation of the corresponding alkenyl cuprates and sulfinamide. The alkenyl cuprates can be trapped by electrophiles. The ACCR presumably proceeds via the formation of a higher-order sulfoximine-substituted alkenyl cuprate, which undergoes a 1,2-metalate rearrangement whereby the sulfoximine group acts as the nucleofuge. The parent (E)- and (Z)-configured alkenyl sulfoximines suffer upon treatment with an organocuprate a deprotonation at the α-position with formation of the corresponding α-cuprioalkenyl sulfoximines. These derivatives also enter into a similar ACCR with organocuprates. The ACCR of sulfoximines substituted homoallylic alcohols allows a stereoselective access to enantio- and diastereopure substituted homoallylic alcohols.

Full text of DOI:10.1002/chem.200800455

DOI: 10.1002/chem.200800455
Anionic Cross-Coupling Reaction of a-Metallated Alkenyl Sulfoximines and
Alkenyl Sulfoximines with Cuprates Featuring a 1,2-Metal-Ate
Rearrangement ofSulof ximine-Substituted Higher Order Alkenyl Cuprates
and an a-Metallation ofAlkenyl Sulof ximines by Cuprates
[a]
Hans-Joachim Gais,* C. Venkateshwar Rao, and RalfLoo
Abstract: (E)- and (Z)-configured a-
lithioalkenyl sulfoximines, which are
available through lithiation of the cor-
responding alkenyl sulfoximines, under-
go a anionic cross-coupling reaction
(ACCR) with organocuprates with for-
mation of the corresponding alkenyl
cuprates and sulfinamide. The alkenyl
cuprates can be trapped by electro-
philes. The ACCR presumably pro-
ceeds via the formation of a higher-
order sulfoximine-substituted alkenyl
cuprate, which undergoes a 1,2-metal-
ate rearrangement whereby the sulfoxi-
mine group acts as the nucleofuge. The
parent (E)- and (Z)-configured alkenyl
sulfoximines suffer upon treatment
with an organocuprate a deprotonation
at the a-position with formation of the
corresponding a-cuprioalkenyl sulfox-
A
into a similar ACCR with organocup-
rates. The ACCR of sulfoximines sub-
stituted homoallylic alcohols allows a
stereoselective access to enantio- and
diastereopure substituted homoallylic
Keywords: asymmetric catalysis
·
cross-coupling · cuprates · lithium ·
metalation
alcohols.
Introduction
ration (see below) and 4a. The conversion of the putative
nickel-ate complex (Z)-3 to the (Z)-configured alkenyllithi-
um derivative (Z)-5 would be an example of a 1,2-metal-ate
rearrangement (1,2-MR) of an alkenyl-ate complex involv-
ing the sulfoximine group as nucleofuge. Previously,
ACCRꢀs involving 1,2-MRꢀs of alkenyl-ate complexes had
been demonstrated for B, Al, Zr, Zn and Cu as metal and
halogen-, alkoxy-, phenylsulfanyl-, carbamoyloxy- and
amino-substituents as nucleofuge[6–14] (Scheme 2). All of
these ACCRꢀs are stoichiometric in the metal except the
one based on Cu for which also a catalytic version has been
described.[11b]
The a-phenyl-substituted alkenyllithium derivative (Z)-5
could not be isolated because of the establishment of an
equilibrium with (E)-5 followed by a 1,5-O,C-Si migration
(MG) of the latter with formation of the alkenylsilane 6. In
the Ni0-catalyzed ACCRꢀs the sulfoximine group showed an
exceptional ability to function as a nucleofuge. Because of a
formal analogy between the nickel-ate complex (Z)-3 and
the higher order (HO) cuprates (E)-7 and (Z)-7 (Scheme 3),
we became interested to see 1) whether HO cuprates of this
type can be generated from (Z)-2 and (E)-2, respectively,
and organocuprates and 2) if they would undergo a stereose-
lective copper-based 1,2-MR[6,11–14] to give the corresponding
lower order (LO) cuprates (Z)-8 and (E)-8, respectively.
Some time ago we had observed that a-lithioalkenyl sulfox-
imines of type (E)-2, which were prepared by lithiation–iso-
G
merization of the alkenyl sulfoximines (Z)-1, readily engage
at 08Cin a Ni 0-catalyzed anionic cross-coupling reaction
(ACCR) with PhLi. The ACCR finally afforded (Z)-config-
ured phenyl-substituted alkenylsilanes of type 6 together
with sulfinamide 4a (Scheme 1).[1–3] This noteworthy Ni0-cat-
alyzed ACCR of a-lithioalkenyl sulfoximines with PhLi is
not restricted to lithioalkenyl sulfoximines of type (E)-2 and
PhLi but can be extended to other a-lithio- and a-magne-
sioalkenyl sulfoximines as well by using lithium- and magne-
siumorganyls.[4,5]
It is assumed that the ACCR proceeds via the formation
of a nickel-ate-complex of type (Z)-3 which undergoes a mi-
gratory insertion/reductive elimination to afford the alkenyl-
lithium derivative (Z)-5,[2,5] having perhaps the (Z)-configu-
[a] Prof. Dr. H.-J. Gais, Dr. C. V. Rao, Dr. R. Loo
Institute of Organic Chemistry, RWTH Aachen University
Landoltweg 1, 52056 Aachen (Germany)
Fax : (+49)2418092665
E-mail: Gais@RWTH-Aachen.de
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FULL PAPER
nyllithium derivatives. There-
fore, a stochiometric ACCR of
(Z)-2 and (E)-2 with organo-
cuprates could give access to
highly substituted homoallyl al-
cohols of type (E)-9 and (Z)-9,
which are not readily available
otherwise.[15,16] This route to
(E)-9 and (Z)-9 should benefit
from 1) the facile synthesis of
copper reagents including those
carrying functional groups;[17] 2)
the high reactivity of alkenyl
cuprates of type (Z)-8 and (E)-
8; and 3) the ready availability
of the alkenyl sulfoximines (Z)-
1 and (E)-1[18–21] as well as their
Scheme 1. Ni0-catalyzed ACCR of a-lithioalkenyl sulfoximines (E)-2 with PhLi (a possible coordination of the
Ni atom of (Z)-3 by PPh3 is not shown).
a-lithio derivatives (Z)-2 and (E)-2, respectively.[1,2,19,22–24]
Support for the feasibility of a synthesis of sulfoximine-
substituted HO alkenyl cuprates of type (E)-7 and (Z)-7
and their 1,2-MR came from studies of the carbamoyloxy-
substituted HO alkenyl cuprates (E)-11 (Scheme 4). It had
been shown that cuprates (E)-11, which were prepared from
the lithiated or stannylated alkenyl carbamates (Z)-10 and
LiCu(R3)2, readily undergo a 1,2-MR with formation of the
alkenyl cuprates (Z)-12, the trapping of which with electro-
philes afforded (E)-9.[6,12]
Scheme 2. 1,2-Metal-ate rearrangement of alkenyl metal derivatives.
This route which can, however, only provide an access to
the (E)-configured homoallyl alcohols (E)-9 is hampered by
the limited stability of the a-lithioalkenyl carbamates (Z)-
10, which suffer an elimination with formation of the corre-
sponding alkynes even at low temperatures.[6,12] In contrast,
Trapping of the latter with electrophiles should afford the
homoallyl alcohols (E)-9 and (Z)-9, respectively.
Alkenylcuprates of type (Z)-8 and (E)-8 should be less
prone to a Z/E isomerization than the corresponding alke-
Scheme 3. Synthesis and 1,2-MR of sulfoximine-substituted HO alkenyl cuprates.
Chem. Eur. J. 2008, 14, 6510 – 6528
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6511

H.-J. Gais et al.
The new, unsaturated alkenyl sulfoximine (Z)-1b was ob-
tained by a similar two step route from 13b and pent-4-enal
via (Z)-14b with ꢀ98% diastereoselectivity and 94% yield,
respectively. Treatment of the alkenyl sulfoximines (Z)-1a–c
with BuLi at ꢁ708Cgave the corresponding ( Z)-configured
alkenyllithium derivatives (Z)-2a–c, which suffered a com-
plete isomerization to the corresponding (E)-isomers (E)-
2a–c upon warming the solution to ꢁ108C. Protonation of
(E)-2a–c with NH4Cl furnished the corresponding (E)-con-
figured isomers (E)-1a–c in almost quantitative yield.
ACCRꢀs ofalkenyl sulfoximines and a-lithioalkenyl
sulfoximines
Scheme 4. Synthesis and 1,2-MR of carbamoyloxy-substituted HO alken-
yl cuprates.
(Z)-Configured alkenyl sulfoximine and organocuprate:
First the reactivity of the alkenyl sulfoximine (Z)-1a to-
the lithioalkenyl sulfoximines (Z)-2 and (E)-2 are stable to-
wards elimination up to room temperature. They are readily
available through lithiation of the corresponding alkenyl sul-
wards LiCuBu2, LiCuMe2, LiCuPh2 and LiCu(CH=CH2)2 in
A
Et2O was studied by applying an excess of the cuprate
(Scheme 6, Table 1).
foximines
(Z)-1
and
(E)-1,
respectively
(cf.
Scheme 3),[1,2,19,22–24] which in turn can be obtained in enan-
tio- and diastereopure via the reaction of the corresponding
enantiopure bis(allylsulfoximine)titanium complexes with al-
dehydes (see below).[18–21]
The cuprates were prepared from CuI and the corre-
sponding lithiumorganyl by using a slight excess of CuI in
order to eventually avoid the presence of the free lithiumor-
ganyl. No reaction was observed between (Z)-1a and
LiCuBu2 at ꢁ408C(Table 1, entry 1). Quenching of the re-
action mixture with D2O led to the quantitative recovery of
the sulfoximine (Z)-1a containing, however, no D atom at
the a-position. Surprisingly, warming up the reaction mix-
ture of (Z)-1a and LiCuBu2 to 08Cand quenching the mix-
ture with D2O furnished the (E)-configured alkene [D]-(E)-
9aa carrying a D atom (ꢀ98%) at the a-position with an
E/Z selectivity of ꢀ44:1 in 47% yield (entry 2). The starting
material (Z)-1a containing no D atom was recovered in
26% yield. Then the reaction of (Z)-1a with LiCuBu2 was
run first at low temperatures and then at 08C. This led to a
higher conversion of sulfoximine (Z)-1a and alkene (Z)-6aa
was isolated in 78% yield with an E/Z selectivity of ꢀ44:1
(entry 3). The starting sulfoximine (Z)-1a was recovered in
13% yield. In a final experiment the reaction mixture ob-
tained from a treatment of (Z)-1a with an excess of
In this paper we describe the ACCR of a-lithioalkenyl
sulfoximines of type (Z)-2 and (E)-2 with organocuprates,
which stereoselectively gives alkenyl cuprates of type (Z)-8
and (E)-8, respectively, via a copper-based 1,2-MR (cf.
Scheme 3). This ACCR has been applied to the stereoselec-
tive synthesis of enantio- and diastereopure homoallyl alco-
hols of type (E)-9 and (Z)-9. We report furthermore about
the surprising observation that the alkenyl sulfoximines (Z)-
1 and (E)-1 are deprotonated upon treatment with organo-
cuprates at the a-position with formation of a-cuprioalkenyl
sulfoximines, which readily undergo a similar ACCR with
organocuprates as (Z)-2 and (E)-2.
Results and Discussion
Asymmetric synthesis ofalken-
yl sulfoximines: The enantio-
and diastereopure sulfoximine-
substituted homoallyl alcohols
(Z)-14a and (Z)-14c were ob-
tained, as previously de-
scribed,[18] from the enantiopure
allyl sulfoximines 13a and 13c,
respectively, through their suc-
cessive treatment with BuLi,
2 equiv of ClTi(OiPr)3 and the
G
corresponding aldehydes in 76
and 81% yield (Scheme 5). Si-
lylation of alcohols (Z)-14a and
(Z)-14c afforded the silyl
ethers (Z)-1a and (Z)-1c in 97
and 95% yield, respectively.
Scheme 5. Asymmetric synthesis of sulfoximine-substituted homoallylic alcohols and a-lithioalkenyl sulfox-
imines.
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Sulfoximines Reactions
FULL PAPER
stereoisomer in low yield.
Having obtained favorable re-
sults in the ACCR of (Z)-1a
with LiCuBu2, LiCuMe2 and
LiCuPh2, the reactivity of the
alkenyl sulfoximine towards
LiCu
Treatment of (Z)-1a with an
excess of LiCu(CH=CH2)2 af-
A
AHCTREUNG
forded diene (E)-9ad in 62%
yield with an E/Z selectivity of
22:1. In this case the (E,E)-con-
figured diene (E,E)-17ab was
formed as a single stereoisomer
in low yield. In all reactions
listed in Table 1 sulfinamide 4b
of ꢀ98% ee was formed in
high yield.
Scheme 6. ACCR of (Z)-configured alkenyl sulfoximines with cuprates and cuprates admixed the correspond-
ing lithiumorganyls.
Table 1. ACCR of the alkenyl sulfoximine (Z)-1a with LiCuR2.
Entry
LiCuR2 (equiv)
Conditions
Derivative (E)-9a [%]
E/Z
(Z)-6a (Z)-1a
[%]
[%]
(Z)-Configured alkenyl sulfox-
[a]
1
2
LiCuBu2 (5)
ꢁ408C , 1 h
a
a
0
–
0
0
97
26
imine, lithiumorganyl and orga-
[a]
LiCuBu2 (7)
ꢁ40!08C , 4 h
47[b]
ꢀ44:1
nocuprate: The isolation of the
fully deuterated alkene [D]-
(E)-9aa and the alkenyl silane
(Z)-6aa from the reaction of
(Z)-1a with an excess of
LiCuBu2 and [D]-(E)-9ab from
the reaction of (Z)-1a with an
(ꢀ98% D)
[a]
3
4
5
LiCuBu2 (7)
ꢁ15!08C , 3 h
ꢁ408C!RT, 18 h
ꢁ408C!RT, 18 h
a
a
b
78
ꢀ44:1
ꢀ44:1
30:1
0
23
0
13
0
[a]
LiCuBu2 (3)
52[b]
75[c]
LiCuMe2 (3)
0[d,e]
(ꢀ98% D)
6
7
LiCuPh2 (4)
ꢁ408C!RT, 18 h
ꢁ158C!RT, 4 h
c
d
85[f]
66[g]
35:1
22:1
0
0
0
0
LiCu
(CH=CH2)2 (2)
[a] n-Butyl cuprate was used. [b] According to GC/MS alkene 15 was formed in low yield. [c] According to
GC/MS alkene 16a was formed in low yield. [d] (E)-1a was isolated in low yield. [e] Work-up with D2O gave
[D]-(E)-1a (ꢀ98% D) in low yield. [f] According to GC/MS diene (E,E)-17aa was formed in low yield.
[g] According to GC/MS diene (E,E)-17ab was formed in low yield.
excess of LiCuMe2 gave
a
strong indication for the opera-
tion of an ACCR involving a
HO cuprate of type (E)-7 and
its conversion to a LO cuprate
LiCuBu2 at ꢁ408Cwas stirred for a longer time at room
temperature. Notably, besides 52% of alkene (E)-9aa the
(Z)-configured alkenyl silane (Z)-6aa was obtained in 23%
yield, both as single stereoisomers (entry 4). Thus, in all ex-
periments the ACCR of the (Z)-configured alkenyl sulfoxi-
mine (Z)-1a proceeded with high E/Z selectivity under in-
version of the configuration of the double bond and afford-
ed the (E)-configured alkene (E)-9aa. In entries 2 and 4 the
unsubstituted alkene 15 was obtained as a side product in
low yield. Next the ACCR of (Z)-1a with LiCuMe2 was
studied. Here the (E)-configured alkene (E)-9ab was ob-
tained in 75% yield with high stereoselectivity (entry 5). In
this case the formation of the corresponding silane (Z)-6ab
and alkene 15 was not observed. The only side product was
the dimethylated alkene 16a which was obtained in low
yield. Interestingly, however, a work-up of the reaction mix-
ture with D2O not only furnished the deuterated alkene
[D]-(E)-9ab (ꢀ98% D) but also allowed the isolation of a
small amount of the alkenyl sulfoximine [D]-(E)-1a being
fully deuterated at the a-position. Under similar reaction
conditions the ACCR of (Z)-1a with LiCuPh2 also proceed-
ed with high stereoselectivity and gave the (E)-configured
alkene (E)-9ac in 85% yield (entry 6). In this case the
(E,E)-configured diene (E,E)-17aa was formed as a single
of type (Z)-8 (cf. Scheme 3) through a stereoselective 1,2-
MR. Thus, in the first step a metalation of the alkenyl sul-
foximine (Z)-1a at the a-position by the organocuprate
must have occurred, in which a a-cuprio analogue of the a-
lithioalkenyl sulfoximine (E)-2a was formed. In order to fur-
ther substantiate this surprising notion and to gain informa-
tion about this reaction, experiments were undertaken in
which a mixture of an excess of LiCu(R3)2 and 0.3 to
0.8 equiv of R3Li was used. It was speculated that the appli-
cation of LiCu(R3)2 in combination with R3Li would first
lead to the formation of the a-lithioalkenyl sulfoximine (E)-
2a which may then react with the cuprate. However, there
was also the possibility of an alteration of the course of the
reaction because of the establishment of an equilibrium be-
tween LiCu(R3)2, R3Li and Li2Cu(R3)3 (see below).[25]
Treatment of the (Z)-configured alkenyl sulfoximine (Z)-
1a with 2 equiv of LiCuBu2 and 0.7 equiv of BuLi in Et2O
first at ꢁ158Cand then at room temperature for 18 h gave
the (E)-configured alkene (E)-9aa with an E/Z selectivity of
only 1.7:1 in 51% yield (Table 2, entry 1, cf. Scheme 6) to-
gether with the (Z)-configured alkenyl silane (Z)-6aa
(21%) as a single isomer. The reaction of (Z)-1a with
5 equiv of LiCuMe2 and 0.8 equiv of LiMe under similar
conditions proceeded also with a low stereoselectivity and
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H.-J. Gais et al.
Table 2. ACCR of the alkenyl sulfoximine (Z)-1a with LiCuR2 and LiR.
Entry LiCuR2/RLi (equiv) Conditions Derivative (E)-9a [%] E/Z (Z)-6a [%] (E)-1a [%]
(2/0.7) ꢁ158C!RT, 18 h
LiCuMe2/MeLi (5/0.8) ꢁ158C!RT, 3 h
LiCuPh2/PhLi (3/0.3)
ꢁ158C!RT, 3 h
cant because of higher tempera-
ture and longer reaction time,
took place. Because of steric
reasons, the Si MR led to a
1
2
3
LiCuBu2/BuLi[a]
A
a
b
c
51
1.7:1
3:1
4.8:1
21
0
74
0
5
0
50[b]
11[c]
selective depletion of the (Z)-
[a] n-BuLi and n-butyl cuprate were used. [b] According to GC/MS alkene 16a was formed in low yield.
[c] According to GC/MS diene (E,E)-17aa was formed in low yield.
configured alkenyl cuprate (Z)-
8 and thus to a diminished E/Z
ratio of alkene (E)-9.
afforded a mixture of alkenes (E)-9ab and (Z)-9ab in a
ratio of 3:1 in 50% yield (entry 2). Here, alkene 16a was
isolated as a minor product. The ACCR of (Z)-1a with
3 equiv of LiCuPh2 and 0.3 equiv of LiPh under the same
conditions gave the (Z)-configured alkenyl silane 6ac in
74% yield as a single stereoisomer and only 11% of a mix-
ture of alkenes (E)-9ac and (Z)-9ac in a ratio of 4.8:1
(entry 3). In addition diene (E,E)-17aa was obtained as a
single stereoisomer, as in the previous experiment with
LiCuPh2, in minor amounts.
Because of the results obtained with the cuprates and the
mixtures of cuprates and the corresponding lithiumorganyls,
the ACCR of (Z)-1a with the organocuprates may be ra-
tionalized as follows (Scheme 7, route A). The cuprate
causes deprotonation/cupration of the alkenyl sulfoximine
(Z)-1 at the a-position to give the sulfoximine-substituted
alkenyl cuprate (E)-18 (see below). Then the (E)-configured
LO cuprate (E)-18 reacts with LiCu(R3)2 to afford the (E)-
configured higher order organocuprate (E)-7. Subsequently,
this cuprate undergoes a stereoselective 1,2-MR with inver-
sion of configuration and elimination of sulfinamide 4a to
yield the (Z)-configured LO cuprate (Z)-8. Protonation and
silyl migration of (Z)-8 furnishes after work-up the (E)-con-
figured alkene (E)-9 and the (Z)-configured vinyl silane
(Z)-6, respectively.
In contrast, the ACCR of the alkenyl sulfoximine (Z)-1
with LiCu(R3)2 and LiR3 may proceed at least in part as fol-
lows (route B). Reaction of (Z)-1 with LiR3 first gives the
(Z)-configured a-lithioalkenyl sulfoximine (Z)-2 which sub-
sequently combines with LiCu(R3)2 to form the HO cuprate
(E)-7. Proof for the formation of the substituted (R3) cup-
rate (Z)-8 as the final product in both routes A and B
comes from 1) the deuteration of (Z)-8aa and (Z)-8ab
which gave alkenes [D]-(E)-9aa and [D]-(E)-9ab, respec-
Scheme 7. Mechanistic rationalization of the ACCR of alkenyl sulfox-
tively, and 2) the stereoselective 1,5-O,C-Si migration (retro-
Brook rearrangement) of (Z)-8aa and (Z)-8ac,[1,11j,26] which
furnished via the corresponding copper alcoholates (Z)-
19aa and (Z)-19ac the alkenyl silanes (Z)-6aa and (Z)-6aa,
respectively. A major difference between the ACCR of (Z)-
1 with LiCu(R3)2 and LiCu(R3)2/LiR3 is the lower E/Z selec-
tivity in the later case. This may be ascribed to the operation
of two effects. First, in route B the isomerization of the a-
lithioalkenyl sulfoximine (Z)-2 to its (E)-configured isomer
(E)-2 may have effectively competed with the reaction of
the former with the cuprate because of the relatively high
reaction temperature. Thus, both the (E)- and (Z)-config-
ured HO cuprates (E)-7 and (Z)-7 could have been formed.
Second, a consecutive 1,5-O,C-Si MR, which became signifi-
imines and a-lithioalkenyl sulfoximines with cuprates.
(Z)-Configured a-lithioalkenyl sulfoximines and organocup-
rates: In order to seek a further confirmation for the pro-
posed formation of the higher order cuprates (E)-7 from the
alkenyllithium derivatives (Z)-2 and LiCu(R3)2 in the reac-
tion of (Z)-1 with LiCu(R3)2/LiR3 (cf. Scheme 7), the a-lith-
ioalkenyl sulfoximine (Z)-2b for example was first generat-
ed upon treatment of (Z)-1b with 1.1 equiv of LiR3 and
then in a second step treated with LiCu(R3)2 (Scheme 8).
Thus, sulfoximine (Z)-1b was treated with LiMe, which
afforded the (Z)-configured lithioalkenyl sulfoximine (Z)-
2b in practically quantitative yield as shown by deuteration.
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Sulfoximines Reactions
FULL PAPER
Scheme 8. ACCR of (Z)-configured alkenyl sulfoximines and a-lithioalkenyl sulfoximines with LiCuMe2.
The reaction of (Z)-2b with LiCuMe2 (3 equiv) at ꢁ408Cto
room temperature gave the (E)-configured alkene (E)-9b
with an E/Z selectivity of ꢀ40:1 and the dimethylated
alkene 16b in a ratio of 7:3 (Table 3, entry 4). No ACCR
was observed between (Z)-2b with LiCuMe2 at ꢁ408C
(entry 1). Instead, the isomeric alkenyl sulfoximines (E)-1b
was isolated in almost quantitative yield. At 08Cthe slow
formation of (E)-9b with an E/Z selectivity of ꢀ40:1 and
16b (entry 2) occurred. The reaction at room temperature
furnished diene (Z,E)-17b as a side product (entries 3–5).
These results give strong support to the mechanistic picture
outlined in Scheme 7 in general and for the intermediacy of
the HO cuprates (E)-7 in particular.
(Z)-1c. The reaction of the alkenyl sulfoximine (Z)-1b with
3 equiv of LiCuMe2 at ꢁ408Cto room temperature afforded
a mixture of the (E)-configured alkene (E)-9b with an E/Z
selectivity of ꢀ40:1 and the dimethylated alkene 16b in a
ratio of 9:1 (Table 4, entry 4). When the same reaction was
run at ꢁ408Cto room temperature for a longer time a mix-
ture of alkene (E)-9b, alkene 16b and diene (Z,E)-17b was
isolated in a ratio of 8:1:1 (entry 5). No ACCR was ob-
served between (Z)-1b and LiCuMe2 (3 equiv) at ꢁ408C
(entry 1). Instead, the (E)-configured alkenyl sulfoximine
(E)-1b was isolated in high yield. The conversion of (Z)-1b
and the formation of (E)-9b, 16b and (Z,E)-17b in the reac-
tion of (Z)-1b with LiCuMe2 showed similar time and tem-
perature dependencies (entries 1–5) as that of (Z)-2b with
LiCuMe2. Thus the ACCR of the a-lithioalkenyl sulfoximine
(Z)-2b and the parent alkenyl sulfoximine (Z)-1b with an
excess of LiCuMe2 gave almost
In order to have a more complete picture the reactivity of
the parent alkenyl sulfoximine (Z)-1b was also studied and
the investigations were extended to the alkenyl sulfoximine
the same results.
Because of the results ob-
tained in the ACCR of the a-
Table 3. ACCR of the a-lithioalkenyl sulfoximine (Z)-2b with LiCuMe2.
Entry
equiv
Conditions
(E)-9b [%]
E/Z
(E)-9b:16b
16b [%]
(E)-1b [%]
lithioalkenyl sulfoximine (Z)-
2b with the cuprate, the analo-
gous reaction of (Z)-2c was
also studied. Treatment of the
alkenyl sulfoximine (Z)-1c with
MeLi quantitatively afforded
1
2
3
4
5
3
3
3
3
3
ꢁ408C, 1 h
0
10
–
100
62
–
–
–
ꢁ40!08C , 4 h
ꢁ408C!RT, 4 h
ꢁ408C!RT, 8 h
ꢁ408C!RT, 12 h
ꢀ40:1
ꢀ40:1
ꢀ40:1
ꢀ40:1
7:3
7:3
7:3
7:3
4
12
18
18
35[a]
41[a]
41[a]
[a] According to GC/MS (Z,E)-17b was formed in low yield.
Chem. Eur. J. 2008, 14, 6510 – 6528
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6515

H.-J. Gais et al.
Table 4. ACCR of the alkenyl sulfoximine (Z)-1b with LiCuMe2.
(E)-Configured alkenyl sulfox-
AHCTREUNG
Entry
equiv
Conditions
(E)-9b [%]
E/Z
(E)-9b:16b
16b [%]
(E)-1b [%]
1
2
3
4
5
3
3
3
3
3
ꢁ408C, 1 h
0
10
–
100
ꢁ40!08C , 4 h
ꢁ408C!RT, 4 h
ꢁ408C!RT, 8 h
ꢁ408C!RT, 10 h
ꢀ40:1
ꢀ40:1
ꢀ40:1
ꢀ40:1
9:1
9:1
9:1
8:1
1
4
10
8
50 kenyl sulfoximines (E)-1a–c
10
37
showed only a low reactivity in
the ACCR with LiCuR2. Practi-
cally no ACCR was observed
between (E)-1a and LiCuBu2 in
Et2O at 08C. Similarly, the
treatment of the alkenyl sulfox-
70[a]
64[a]
[a] According to GC/MS (Z,E)-17b was formed in low yield.
the lithioalkenyl sulfoximine (Z)-2c as shown by deutera-
tion. The ACCR of (Z)-2c with LiCuMe2 (3 equiv) gave a
mixture of the (E)-configured alkene (E)-9c with an E/Z se-
lectivity of ꢀ40:1 and the dimethylated alkene 16c in a
ratio of 7:3 (Table 5, entry 4). In a similar ACCR of (Z)-2c
with LiCuMe2 the mixture was quenched with D2O after the
indicated reaction time, which led to the isolation of alkene
(E)-9c with an E/Z selectivity of ꢀ40:1 being fully deuterat-
ed at the a-position. No reaction was observed between (Z)-
1c and LiCuMe2 (3 equiv) at ꢁ408C(entry 1). Instead, the
(E)-configured alkenyl sulfoximine (E)-1c was isolated in
high yield. The conversion of (Z)-2c and the formation of
(E)-9c and 16c in the reaction of (Z)-2c with LiCuMe2
showed similar time and temperature dependencies (en-
tries 1–5) as that of (Z)-2b with LiCuMe2. These results give
further proof for the formation of LO alkenyl cuprates of
type (E)-8 (cf. Scheme 7) in the ACCR of the a-lithioalken-
yl sulfoximines (E)-2 with cuprates.
In a final set of experiments the (Z)-configured alkenyl
sulfoximine (Z)-1c was subjected to reaction with 3 equiv of
LiCuMe2, at various temperatures and different reaction
times (Table 6, entries 1–5). A mixture of alkenes (E)-9c
with an E/Z selectivity of ꢀ40:1 and 16c was obtained at
room temperature in a ratio of 9:1 (entry 4). In a similar
ACCR of ( Z)-1c with LiCuMe2 the reaction mixture was
quenched with D2O. This led to the isolation of alkene (E)-
9cb with an E/Z selectivity of ꢀ40:1 being fully deuterated
at the a-position. No reaction was observed between (Z)-1c
and LiCuMe2 (3 equiv) at ꢁ408C(entry 1). Instead, the ( E)-
configured alkenyl sulfoximine (E)-1c was isolated in high
yield. A further confirmation of
imine (E)-1c with 3 equiv of LiCuMe2 at ꢁ408Cto room
temperature led to the recovery of (E)-1c in high yield
(Scheme 9) (Table 7, entries 1–3). In the experiment with
(E)-1c at room temperature the a-methylated alkenyl sul-
foximine (E)-22 was obtained in 10% yield (entry 3). Sur-
prisingly, however, a D2O quench of the mixture led to the
isolation of the starting alkenyl sulfoximine [D]-(E)-1c
G
being deuterated at the a-position (90%). Finally, the appli-
cation of both 10 equiv of LiCuMe2 and room temperature
saw a complete conversion of the alkenyl sulfoximine (E)-
1c and gave in a highly stereoselective ACCR a mixture of
the alkenes (Z)-9c with a Z/E selectivity of ꢀ40:1 and 16c
in a ratio of 9:1 (entries 4 and 5).
These results give direct proof for a metalation of the
(E)-configured alkenyl sulfoximine (E)-1a–c by LiCu(R3)2
at the a-position with formation of (Z)-18 (cf. Scheme 7).
Because of the similarity in the reactivity of (E)-1 and (Z)-1
in the ACCR with LiCu(R3)2, it can safely be assumed that
the (E)-configured alkenyl sulfoximines (E)-1 are also first
metalated by the cuprate at the a-position.
(E)-Configured a-lithioalkenyl sulfoximines and organocup-
rates: Having observed a surprisingly low reactivity of the
(E)-configured alkenyl sulfoximines (E)-1 in the ACCR
with cuprates and obtained evidence for their a-metalation
by the cuprates, it was of interest to study the ACCR of the
corresponding (E)-configured a-lithioalkenyl sulfoximines
(E)-2 with organocuprates. Treatment of (E)-1a with an
excess of LiCuPh2 and PhLi at room temperature stereo-
A
the formation of the LO cup-
Table 5. ACCR of the a-lithioalkenyl sulfoximine (Z)-2c with LiCuMe2.
rate (E)-8cb in this ACCR was
provided by its conjugate addi-
tion to ethyl acrylate. Thus, the
alkenyl sulfoximine (Z)-1c was
first treated at ꢁ408Cwith
3 equiv of LiCuMe2 and the
mixture was warmed to room
temperature. Then ethyl acry-
late was added at ꢁ408Cand
the mixture was warmed to
room temperature. This led to
the isolation of the ester (Z)-20
having a (Z)-configured trisub-
stituted double bond in 50%
yield.
Entry
equiv
Conditions
(E)-9c [%]
E/Z
(E)-9c:16c
16c [%]
(E)-1c [%]
1
2
3
4
5
3
3
3
3
3
ꢁ408C, 1 h
0
7
39
50
43
–
–
–
1
8
19
14
100
70
12
–
ꢁ40!08C , 4 h
ꢁ408C!RT, 4 h
ꢁ408C!RT, 8 h
ꢁ408C!RT, 10 h
ꢀ40:1
ꢀ40:1
ꢀ40:1
ꢀ40:1
7:3
7:3
7:3
7:3
–
Table 6. ACCR of the alkenyl sulfoximine (Z)-1c with LiCuMe2.
Entry
equiv
Conditions
(E)-9c [%]
E/Z
(E)-9c:16c
16c [%]
(E)-1c [%]
1
2
3
4
5
3
3
3
3
3
ꢁ408C, 1 h
0
8
41
–
100
75
10
–
ꢁ408C!08C , 4 h
ꢁ408C!RT, 4 h
ꢁ408C!RT, 8 h
ꢁ408C!RT, 10 h
ꢀ40:1
ꢀ40:1
ꢀ40:1
ꢀ40:1
9:1
9:1
9:1
9:1
1
4
9
6
71 (98% D)
62
–
6516
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Chem. Eur. J. 2008, 14, 6510 – 6528

Sulfoximines Reactions
FULL PAPER
Scheme 9. ACCR of (E)-configured alkenyl sulfoximines and a-lithioalkenyl sulfoximines with LiCuMe2.
Table 7. ACCR of the alkenyl sulfoximine (E)-1c with LiCuMe2.
diene (Z,Z)-17aa, respectively.
Dienes (E,E)-17aa and (Z,E)-
17ab (cf. Scheme 6) could be
derived from the isomer (Z)-2a
by a similar pathway.
These results indicate that
(E)-configured a-lithioalkenyl
sulfoximines are also capable to
Entry
equiv
Conditions
(Z)-9c [%]
Z/E
(Z)-9c:16c
16c [%]
(E)-1c [%]
1
2
3
4
5
3
3
3
10
10
ꢁ408C, 1 h
0
0
–
–
9:1
9:1
9:1
100
100
80 (90% D)
12
–
ꢁ40!08C, 4 h
ꢁ408C!RT, 4 h
ꢁ408C!RT, 12 h
ꢁ408C!RT, 20 h
–
2[a]
59
72
ꢀ40:1
ꢀ40:1
ꢀ40:1
–
5
7
1
[a] According to H NMR 22 was formed in 10% yield.
undergo
a
stereoselective
ACCR with organocuprates. In
a Z/E selectivity of 15:1 in 60% yield and diene (Z,Z)-17aa
as a single stereoisomer in 30% yield (cf. Scheme 9). The
formation of diene (Z,Z)-17aa, the extend of which in-
creased with increasing concentration of (E)-2a, is remark-
able. These results suggest the operation of two consecutive
stereoselective 1,2-MRꢀs of the sulfoximine-substituted HO
cuprates (Z)-7ac and 23 (Scheme 10, routes A and B). Lith-
iation of (E)-1a with PhLi affords the (E)-configured a-lith-
ioalkenyl sulfoximine (E)-2a which reacts with LiCuPh2
with formation of the (Z)-configured HO phenyl-substituted
cuprate (Z)-7ac, the stereoselective 1,2-MR of which gives
the (E)-configured LO cuprate (E)-8ac. The lower order
cuprate (E)-8ac remains as such (route A) or, in a compet-
ing slow reaction, combines with the (E)-configured a-lith-
ioalkenyl sulfoximine (E)-2a to yield the (E,Z)-configured
HO cuprate 23 (route B) which in turn suffers a stereoselec-
tive 1,2-MR and gives the (E,Z)-configured LO cuprate 24.
Protonation of (E)-8ac and 24 yield alkene (Z)-9ac and
order to further substantiate this notion the reactivity of the
(E)-configured a-lithioalkenyl sulfoximines (E)-2b and (E)-
2c was studied. The alkenyllithium derivative (E)-2c was
obtained in almost quantitative yield through lithiation of
(E)-1c with MeLi as shown by deuteration. Almost no reac-
tion was observed between (E)-2c and 3 equiv of LiCuMe2
at ꢁ408C , 08Cand room temperature (Table 8, entries 1–3).
The starting alkenyl sulfoximine (E)-1c was recovered in
high yield. Only the treatment of (E)-2c with 10 equiv of
LiCuMe2 at room temperature for a prolonged period of
time furnished a mixture of the (Z)-configured alkene (Z)-
9c with a Z/E selectivity of ꢀ40:1 and alkene 16c in a ratio
of 7:3 (entries 4 and 5). A similar ACCR was observed in
the case of (E)-2b. Lithiation of the alkenyl sulfoximine
(E)-1b with MeLi afforded the (E)-configured lithiated al-
kenyl sulfoximine (E)-2b. Treatment of (E)-2c with
10 equiv of LiCuMe2 at room temperature followed by the
addition of D2O gave a mixture of alkene (Z)-9b, being
Chem. Eur. J. 2008, 14, 6510 – 6528
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6517

H.-J. Gais et al.
Scheme 10. Mechanistic rationalization of the formation of side products in the ACCR of a-lithioalkenyl sulfoximines with cuprates.
imines (E)-1 and (Z)-1 by cup-
rates with formation of the sul-
Table 8. ACCR of the a-lithioalkenyl sulfoximine (E)-2c with LiCuMe2.
Entry
equiv
Conditions
(Z)-9c [%]
Z/E
(Z)-9c:16c
16c [%]
(E)-1c [%]
foximine-substituted
alkenyl
1
2
3
4
5
3
3
3
10
10
ꢁ408C, 1 h
0
0
–
–
100
100
80
10
–
cuprates (Z)-18 and (E)-18.
Scheme 7 (see above) shows
the mechanistic picture for the
ACCR of the (Z)-configured
substrates (Z)-1 and (Z)-2. A
similar mechanistic picture is
proposed for the stereoselective
ꢁ408C!08C, 4 h
ꢁ408C!RT, 4 h
ꢁ408C!RT, 12 h
ꢁ408C!RT, 20 h
2[a]
42
52
ꢀ40:1
ꢀ40:1
ꢀ40:1
–
7:3
7:3
–
11
23
1
[a] According to H NMR (E)-22 was formed in low yield.
fully deuterated at the a-position with an E/Z selectivity of
ꢀ40:1 and alkene 16b in a ratio of 7:3.
ACCR of the (E)-configured isomers (E)-1 and (E)-2 (not
shown). It should be emphasized, however, that a definite
structural proof for the sulfoximine-substituted higher order
alkenyl cuprates (E)-7 and (Z)-7 as depicted in Schemes 2, 7
and 10 featuring a dianionic tricoordinate Cu atom, is lack-
The ACCR of the alkenyl sulfoximines (Z)-1a, (Z)-1b,
(Z)-1c and (E)-1c as well as that of the a-lithioalkenyl sul-
foximines (Z)-2b, (Z)-2c and (E)-2b with LiCuMe2 gave
considerable amounts of the dimethylated alkenes 16a–c, re-
spectively, besides the corresponding monomethylated al-
kenes. In addition the reaction of the alkenyl sulfoximine
(E)-1c with LiCuMe2 gave a small amount of the a-methy-
lated alkenyl sulfoximine (E)-22 (cf. Schemes 8 and 9). For-
mation of these methylated alkenes can perhaps be ex-
plained by an oxidation of the intermediate cuprates (Z)-8,
(E)-8 and (Z)-18, respectively,[27,28] as exemplified for (Z)-
18c and (Z)-8c in Scheme 10. Either sulfinamide 4a[29] or
the starting sulfoximine could act as an oxidant.[30]
ing. Although HO cuprates with a trivalent dianionic Cu
A
atom have frequently been proposed as key intermediates
for example in the ACCRꢀs of a-lithioenol ethers,[6,11] a-lith-
ioalkenyl carbamates[6,12] and a-lithioalkenyl sulfides,[14]
a
direct proof for their existence is not available. The exis-
tence of HO cuprates with three negatively charged organic
moieties bound directly to a CuI atom has been demonstrat-
ed for the phenyl derivatives [Li
A
G
N
and [Li3(CuPh2)(CuPh3)(SMe2)4] in the crystal and in solu-
A
N
ACHTREUNG
tion.[25,31,32] However, the structural evidence that had been
obtained for the existence of trialkyl-substituted HO cup-
rates in solution is ambiguous.[25,33–35] Ab initio calculations
of a complex between the LO cuprate LiCuMe2 and LiMe
for example led to an energy minimum structure containing
a six-membered ring composed of a dimethylcopper unit
coupled to a dilithium–methyl bridge.[36] The alternative
structure of a HO cuprate with the three methyl groups
bound to the Cu atom was found to be much higher in
energy. This brings about the question of a possible alterna-
tive mechanism for the ACCRꢀs of alkenyl sulfoximines and
Mechanistic considerations: The experimental data obtained
from the ACCRꢀs of the alkenyl sulfoximines (Z)-1, (E)-1
and their a-lithio derivatives (Z)-2 and (E)-2 with organo-
cuprates in combination with the results of the intermolecu-
lar trapping experiments with D2O and ethyl acrylate and
the intramolecular trapping with the silyl group are consis-
tent with 1) the stereoselective formation of HO cuprates of
type (Z)-7 and (E)-7; 2) their stereoselective 1,2-MR; and
3) the direct deprotonation/cupration of the alkenyl sulfox-
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Chem. Eur. J. 2008, 14, 6510 – 6528

Sulfoximines Reactions
FULL PAPER
lithiated alkenyl sulfoximines with cuprates, which does not
involve higher order cuprates of type 7 undergoing a stereo-
selective 1,2-MR. For example, it could be proposed that
the reaction of the alkenyl sulfoximine (Z,E)-1 and the lithi-
ated alkenyl sulfoximine (Z,E)-2 with organocuprates only
leads to the formation of a LO cuprate of type (Z,E)-18
(Scheme 11). Then these cuprates could suffer an a-elimina-
tion with formation of the alkylidene carbene 25 and hetero-
cuprate 26. Carbene 25 could subsequently react with
LiCuR2 to give the lower order cuprate (Z,E)-8. However,
there are two observations speaking against such a mecha-
nism. First, we had previously generated alkylidene carbenes
25 through an a-elimination of aminosulfoxonium salts 27[37]
and observed that they suffer a fast 1,2-H-atom shift even at
low temperatures with formation of the alkynes 28. Second,
it would be rather difficult to rationalize how carbene 25
generated from (E)-18 should stereoselectively give the (Z)-
configured cuprate (Z)-8 while the same carbene derived
from (Z)-18 should stereoselectively afford the (E)-config-
ured isomer (E)-8. Therefore, an a-elimination of (Z,E)-18
is not a liable pathway. Alternatively, it could be argued that
the LO cuprate (E)-18 rather than being converted to the
HO cuprate (E)-7 undergoes a stereoselective 1,2-MR with
formation of the alkenyl heterocuprates (Z)-29, the reaction
of which with electrophiles could also lead to the alkenes
that have been isolated. A similar reaction would serve to
convert (Z)-18 into (E)-29 (not shown I Scheme 11). How-
ever, it is unlikely that LO cuprate (Z,E)-18 undergoes a
1,2-MR. It has been demonstrated, for example, that the
phenylsulfanyl-substituted LO cuprate 30 is not capable of
undergoing a 1,2-MR.[14] In contrast, the HO cuprate 31,
which was obtained through treatment of 30 with nBuLi, un-
derwent a 1,2-MR with formation of the LO cuprate 32.
An interesting and surprising feature of the ACCR of
(Z)-1 and (E)-1 with LiCu(R3)2 is the ready deprotonation
the alkenyl sulfoximines by the cuprate at the a-position.
We are not aware of any report describing the deprotona-
tion of a functionalized alkene at the a-position upon action
of an organocuprate with formation of the corresponding al-
kenyl cuprate. Alkenyl cuprates carrying a carbanion-stabi-
lizing functional group at the a-position as for example a
sulfoximine,[38] sulfinyl[39,40] or sulfonyl group[39] have so far
been obtained through a carbocupration of the correspond-
ing functionalized alkynes.[35]
Why do alkenyl sulfoximines of type 1 engage in such a
reaction with cuprates. Sulfoximines are capable to react
with Lewis and Brønsted acids at the N atom of the sulfox-
imine group. Thus, the dimeric cuprate 33 may coordinate
via the Li atom to the sulfoximine group of the alkenyl sul-
foximine (Z)-1[30] (Scheme 12) with formation of complex
(Z)-34. This complex could then undergo an intramolecular
deprotonation/cupration at the a-position to afford (E)-18/
LiCu(R3)2 which can be regarded as a complex between
(E)-18 (cf. Scheme 7) and LiCu(R3)2. Then LiCu(R3)2 reacts
Scheme 11. Alternative mechanistic rationalization for the ACCR of alkenyl sulfoximines and a-lithioalkenyl sulfoximines with cuprates.
Chem. Eur. J. 2008, 14, 6510 – 6528
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6519

H.-J. Gais et al.
tures of [Li5
A
(CuPh3)
G
N
A
ACHTREUNG
with the stereoselective 1,2-MR of (E)-7/LiCu(R3)2 to give
the lower order cuprate (Z)-8 which forms a complex with
LiCu(R3)2. A similar sequence of events would serve to con-
vert the (E)-configured alkenyl sulfoximine (E)-1 via (E)-
29, (Z)-18/LiCu(R3)2 and (Z)-7/LiCu(R3)2 to (E)-8/
LiCu(R3)2 (not shown in Scheme 12). The (Z)-configured al-
kenyl sulfoximines (Z)-1 show a significantly higher reactivi-
ty in the ACCR with cuprates than their (E)-configured iso-
mers (E)-1. This could be ascribed to a different rate of cup-
ration of (Z)-1 and (E)-1 with formation of the lower order
cuprates (E)-18 and (Z)-18, respectively. However, the same
difference in reactivity was found for the lithiated alkenyl
sulfoximines (Z)-2 and (E)-2. Thus the different behavior
may be due to differences in the formation of (E)-7 and
(Z)-7 either via route A from (E)-18 and (Z)-18, respective-
ly, or route B (cf. Scheme 7) from (Z)-2 and (E)-2, respec-
tively. Finally, complex (E)-7/LiCu(R3)2 could also undergo
the 1,2-MR faster than complex (Z)-7/LiCu(R3)2 because of
an intramolecular complexation of the Li or Cu atom by the
silyloxy group in the latter case (cf. Scheme 12).
Conclusion
(Z)- and (E)-Configured a-lithioalkenyl sulfoximines of
type 2 readily undergo a highly stereoselective anionic
cross-coupling reaction with organocuprates. This reaction,
which proceeds under inversion of configuration of the
double bond, allows a stereoselective synthesis of (E)- and
(Z)-configured substituted homoallyl alcohols in good
yields. The key step of the cross-coupling reaction is a ste-
reoselective 1,2-metal-ate rearrangement of the correspond-
ing a-sulfoximine-substituted HO alkenyl cuprates. An
intra- or intermolecular trapping of the thereby formed al-
kenyl cuprates with electrophiles gives a stereoselective
access to disubstituted homoallyl alcohols. Although there is
experimental evidence speaking for the involvement of HO
alkenyl cuprates in the 1,2-metal-ate rearrangement, direct
structural proof for their formation has thus fare not been
obtained. Not only a-lithioalkenyl sulfoximines but also the
parent alkenyl sulfoximines can participate in a highly ste-
reoselective ACCR with organocuprates. This type of
ACCR commences with an unprecedented metalation of the
alkenyl sulfoximine by the cuprate at the a-position with
formation of a a-sulfoximine-substituted alkenyl cuprate,
which could be trapped with electrophiles. Apparently the
reaction of the a-cuprioalkenyl sulfoximine and that of the
corresponding a-lithioalkenyl sulfoximine with LO cuprates
leads to the formation of the same sulfoximine-substituted
HO alkenyl cuprate, which subsequently suffers the 1,2-met-
alate rearrangement. The rapid formation of sulfoximine-
substituted LO alkenyl cuprates from the corresponding al-
kenyl sulfoximines upon reaction with a cuprate offers an
explanation for their, at a first glance, surprising failure to
undergo a conjugate addition with the latter.
Scheme 12. a-Deprotonation of alkenyl sulfoximines by cuprates (a possi-
ble coordination of the Li atoms of the various species by solvent mole-
cules is not shown).
with complex (E)-18/LiCu(R3)2 under transfers of LiR3 with
formation of the HO cuprate (E)-7/LiCu(R3)2. A similar
mechanistic Scheme could be proposed for the reaction of
the (E)-configured isomers (E)-1 (not shown). Alternatively,
the deprotonation of the alkenyl sulfoximine (Z)-1 could be
caused by LiR3 being perhaps in equilibrium with the dimer-
ic cuprate [Scheme 12, Eq. (1)][25,35,41] with formation of (Z)-
2
[Eq. (2)]. The subsequent reaction of (Z)-2 with
LiCu2(R3)3 would also lead to the alkenyl cuprate (E)-7/
LiCu(R3)2 [Eq. (3)]. However, the distinction between the
two mechanisms may be superfluous.
The facile deprotonation/cupration of the alkenyl sulfox-
imines (Z)-1 and (E)-1 upon reaction with cuprates via a
prior complexation of the cuprate by the sulfoximine group
explains the surprising failure of the alkenyl sulfoximines to
undergo a conjugate addition with cuprates. The LO sulfox-
A
metalated species not expected to undergo a conjugate addi-
tion easily. Cuprate (E)-7/LiCu(R3)2 is characterized by a
tricoordinate Cu atom, the organic residues of which are
each coordinated to a Li atom and a dicoordinate Cu atom.
Such structural motifs had been found in the crystal struc-
6520
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Chem. Eur. J. 2008, 14, 6510 – 6528

Sulfoximines Reactions
FULL PAPER
(m), 1276 (m), 1248 (vs), 1190 (m), 1153 (vs), 1130 (s), 1070 (s), 1010 (s),
990 (s), 966 (s), 940 (m), 897 (m), 872 (s), 852 (m), 813 cmꢁ1 (m); elemen-
tal analysis calcd (%) for C21H37NO2SSi (395.68): C63.75, H 9.42, N 3.54,
found: C63.83, H 9.35, N 3.51.
Experimental Section
General: All reactions were carried under an argon atmosphere in dry
solvents with syringe and Schlenk techniques in oven-dried glassware.
The alkenyl sulfoximines (Z)-1a and (Z)-1c were prepared according to
the literature.[18–22] THF and Et2O were distilled under argon from lead/
sodium in the presence of benzophenone. CH2Cl2 and DMF were dis-
tilled from CaH2. CuI was purified according to the literature.[42] Bulk
solvents for column chromatography and extractions were distilled prior
to use. Reagents were obtained from commercial sources and used di-
rectly without further purification unless otherwise specified. nBuLi,
MeLi and PhLi were obtained from commercial sources and standardized
by titration with diphenylacetic acid. Vinyllithium was prepared accord-
ing to the literature[43] and standardized by titration with diphenylacetic
acid. TLCwas performed on E. Merck pre-coated plates (silica gel 60
F254, layer thickness 0.2 mm) and chromatography was performed with
E. Merck silica gel (0.040–0.063 mm) in the flash mode with a positive ni-
trogen pressure. HPLCwas carried out with a Dynamax SD-1 pump by
using Varian 320 UV/VIS and Knauer RI detectors by using a chromasil
Si-100 column. Melting points were determined with a Büchi 535 appara-
tus and are uncorrected. 1H and 13CNMR spectra were recorded on
Varian mercury 300 and Varian Inova 400 instruments. Chemical shifts
are reported relative to TMS (0.00 ppm) as internal standard. The follow-
ing abbreviations are used to designate the multiplicity of the peaks in
1H NMR spectra: s= singlet, d= doublet, t= triplet, q= quartet, sex=
sextet, sep= septet, o= octet, m= multiplet, br= broad and combina-
tion thereof. Peaks in the 13CNMR spectra were denoted as “u” for car-
bons with zero or two protons attached or as “d” for carbons with one or
three attached protons, as determined from the APT pulse sequence. As-
signments in the 1H NMR spectra were made by GMQCOSY, GNOE
and HETCOR experiments and those in the 13CNMR spectra were
made by DEPT experiments. IR spectra were recorded on a Perkin–
Elmer PE 1759 FT instrument, and the abbreviations used to designate
the intensity of the peaks are vs= very strong, s= strong, m= medium,
and w= weak. High resolution mass spectra were recorded either on a
Varian MAT 95 Spectrometer or on a Micromass LCT Spectrometer
(ESI, TOF). Optical rotations were measured on a Perkin–Elmer 241 po-
larimeter at approximately 228C. Specific rotation is in grad”mL per
dm”g, and c is in g/100 mL. GC: Chrompack CP-9000, H2; column DB 5
(Carlo Erba) 50 m”0.32 mm, 0.25 mm; temperature program: S 1: 1008C,
5 min, 20 Kminꢁ1, 2508C, 5 min, 30 Kminꢁ1, 3008C, 15 min. S 2: 508C,
A
dien-4-ol [(Z)-14b]: nBuLi (2.22 mL of 1.60m solution in hexane,
3.6 mmol) was added at ꢁ788Cto a solution of the allyl sulfoximine ( E)-
13b (700 mg, 3.3 mmol) in THF (10 mL). After the mixture was stirred
for 10 min at ꢁ788C, ClTi
A
6.9 mmol) was added. The mixture was stirred for 10 min at ꢁ788C, al-
lowed to warm to room temperature and stirred for 45 min at this tem-
perature. Then it was cooled to ꢁ788Cand 4-pentenal (300 mg,
3.6 mmol) was added. The mixture was stirred for 2 h at ꢁ788Cand then
slowly allowed to warm to room temperature over a period of 3 h. Then
it was poured into saturated aqueous (NH4)2CO3 and extracted with
EtOAc. The combined organic phases were dried (MgSO4) and concen-
trated in vacuo. Purification by chromatography (hexane/EtOAc 60:40)
gave the hydroxy sulfoximine (Z)-14b (650 mg, 66%) as colorless crys-
tals. M.p. 728C ; [a]D = ꢁ111.1 (c= 1.4 in CH2Cl2); 1H NMR (400 MHz,
CDCl3): d = 0.86 (d, J = 6.4 Hz, 3H), 1.43–1.57 (m, 1H), 1.67–1.80 (m,
1H), 2.14–2.39 (m, 2H), 2.66 (s, 3H), 3.41 (ddd, J = 10.5, 7.9, 2.97 Hz,
1H), 3.52–3.65 (m, 1H), 3.80 (brs, 1H, OH), 4.96–5.12 (m, 2H), 5.80–
5.94 (m, 1H), 6.15 (t, J = 10.9 Hz, 1H), 6.43 (d, J = 10.9 Hz, 1H), 7.50–
7.64 (m, 3H, Ph), 7.89–7.94 ppm (m, 2H); 13CNMR (100 MHz, CDCl 3):
d = 16.5 (d), 29.2 (d), 29.5 (u), 34.6 (u), 38.4 (d), 74.3 (d), 114.7 (u),
128.8 (d), 129.3 (d), 131.7 (d), 132.8 (d), 138.7 (d), 139.7 (u), 147.9 ppm
(d); IR (KBr): n˜ = 3229 (w), 2971 (m), 2928 (m), 2799 (m), 1618 (w),
1446 (w), 1249 (w), 1215 (w), 1153 (w), 1108 (w), 1001 (m), 961 (s),
910 cmꢁ1 (m); MS (EI, 70 eV): m/z (%): 294 (6) [M++1], 276 (8), 238
(20.0), 195 (35), 125 (100), 109 (18), 107 (31), 77 (25), 55 (39); HRMS
(EI, 70 eV): m/z: calcd for C16H23NO2S: 293.1449 [M+]; found: 293.1450.
Triethyl (Z,3R,4S)-3-methyl-1-[(S)-N-methyl-(S)-phenylsulfonimidoyl]-
octa-1,7-dien-4-yloxy)silane [(Z)-1b]: to a solution of alcohol (Z)-14b
(150 mg, 0.5 mmol) in CH2Cl2 (5 mL) imidazole (103 mg, 1.5 mmol) and
ClSiEt3 (92 mg, 0.6 mmol) were successively added. After the mixture
was stirred for 10 h at room temperature, half-saturated aqueous
NaHCO3 was added and the mixture was extracted with CH2Cl2. The
combined organic phases were dried (MgSO4) and concentrated in vacuo.
Purification by chromatography (hexane/EtOAc 80:20) afforded the silyl
ether (Z)-1b (198 mg, 97%) as a colorless liquid. [a]D = ꢁ81.3 (c= 1.1
1
in CH2Cl2); H NMR (400 MHz, CDCl3): d = 0.49–0.55 (m, 6H), 0.56 (d,
5 min, 30 Kminꢁ1, 1508C, 2 min, 20 Kminꢁ1, 2508C, 2 min, 10 Kminꢁ1
3008C, 15 min.
,
J = 6.86 Hz, 3H), 0.86 (t, J = 7.69 Hz, 9H), 1.38–1.46 (m, 1H), 2.01–
2.13 (m, 1H), 2.60 (s, 3H, NMe), 3.39–3.49 (m, 1H), 3.55 (ddd, J = 9.3,
6.6 Hz, 1H), 4.86–4.90 (m, 1H), 4.97 (dq, J = 3.6 Hz, 1H), 5.67–5.78 (m,
1H), 6.21 (t, J = 11.0 Hz, 1H), 6.31 (d, J = 11.0 Hz, 1H), 7.42–7.52 (m,
3H, Ph), 7.81–7.86 ppm (m, 2H); 13CNMR (100 MHz, CDCl 3): d = 5.3
(u), 7.1 (d), 16.0 (d), 29.3 (d), 29.8 (u), 35.0 (u), 36.1 (d), 74.8 (d), 114.5
(u), 128.7 (d), 129.1 (d), 131.1 (d), 132.3 (d), 138.4 (d), 140.6 (u),
147.5 ppm (d); IR (neat): n˜ = 3065 (m), 2951 (w), 2879 (w), 1637 (s),
1451 (m), 1245 (s), 1149 (w), 1011 (w), 911 (m), 865 (m), 741 (w), 694
(m), 538 cmꢁ1 (m); MS (EI, 70 eV): m/z (%): 407 (2), 378 (76), 352 (87),
270 (25), 195 (85), 115 (100), 87 (75); HRMS (EI, 70 eV): m/z: calcd for
C22H37NO2SSi: 407.2314 [M+]; found: 407.2311.
Triethyl (ꢁ)-(E,2S,3R)-3-isopropyl-5-[(S)-N-methyl-phenylsulfonimido-
yl)]-pent-4-en-2-yloxy)silane [(E)-1a]: MeLi (0.50 mL of 1.60m solution
in Et2O, 0.80 mmol) was added at ꢁ788Cto a solution of sulfoximine
(Z)-1a (212 mg, 0.54 mmol) in Et2O (20 mL). After the mixture was
stirred at ꢁ358Cfor 2 h, saturated aqueous NH 4Cl (10 mL) was added.
The mixture was extracted several times with Et2O and the combined or-
ganic phases were dried (MgSO4) and concentrated in vacuo. Purification
by chromatography (EtOAc/hexane 4:1) gave the alkenyl sulfoximine
(E)-1a (210 mg, 99%) as
a colorless oil. Rf = 0.55 (EtOAc/hexane
80:20); [a]D = ꢁ81.9 (c= 1.25 in CH2Cl2); GC: tR = 12.83 min (S2);
1H NMR (300 MHz, CDCl3): d = 0.47 (brq, J = 7.9 Hz, 6H), 0.82 (d, J
= 6.7 Hz, 3H), 0.87 (t, J = 7.9 Hz, 9H), 0.93 (d, J = 6.7 Hz, 3H), 0.94
(d, J = 6.1 Hz, 3H), 1.73 (m, 1H), 1.86 (o, J = 6.7 Hz, 1H), 2.77 (s, 3H),
4.00 (qd, J = 6.1, 3.9 Hz, 1H), 6.28 (d, J = 15.1 Hz, 1H), 6.76 (dd, J =
15.1, 10.4 Hz, 1H), 7.46–7.58 (m, 3H), 7.90 ppm (m, 2H); 13CNMR
(75 MHz, CDCl3): d = 5.1 (u), 6.9 (d), 20.2 (d), 20.3 (d), 22.9 (d), 28.2
(d), 29.6 (d), 57.3 (d), 68.0 (d), 128.5 (d), 129.2 (d), 132.2 (d), 132.4 (d),
140.1 (u), 147.6ppm (d); GC-MS (EI, 70 eV): m/z (%): 396 [M+] (100),
394 (17), 380 (16), 367 (14), 366 (29), 352 (35), 340 (19), 322 (11), 270
(17), 258 (39), 240 (30), 225 (18), 197 (15), 191 (12), 156 (18), 131 (37),
125 (32), 116 (13), 115 (55), 111 (13), 109 (23), 107 (22), 103 (56), 93 (16),
87 (38), 81 (23), 79 (17), 77 (20), 75 (36), 69 (11), 67 (17), 59 (45), 55
(16), 51 (21); IR (capillary): n˜ = 3387 (w, br), 3063 (vs), 2958 (s), 2935
(s), 2910 (s), 2875 (vs), 2801 (m), 2732 (w), 1963 (w), 1815 (w), 1628 (w),
1583 (s), 1458 (s), 1446 (s), 1417 (s), 1386 (m), 1375 (m), 1356 (m), 1324
Triethyl (E,3R,4S)-3-methyl-1-[(S)-N-methyl-(S)-phenylsulfonimidoyl]oc-
ta-1,7-dien-4-yloxy)silane [(E)-1b]: nBuLi (0.2 mL of 1.6m solution in
hexane, 0.26 mmol) was added at ꢁ788Cto a solution of the vinyl sulfox-
imine (Z)-1b (100 mg, 0.24 mmol) in THF (5 mL). After the mixture was
stirred at ꢁ308Cfor 1 h, it was quenched with saturated NH 4Cl and ex-
tracted with EtOAc. The combined organic phases were dried (MgSO4)
and concentrated in vacuo. Purification by chromatography (hexane/
EtOAc 80:20) gave (E)-1b (82 mg, 82%) as an oily liquid. [a]D = +11.7
(c= 2.0 in CH2Cl2); 1H NMR (400 MHz, CDCl3): d
= 0.49–0.56 (m,
6H), 0.90 (t, J = 7.9 Hz, 9H), 1.05 (d, J = 6.9 Hz, 3H), 1.27–1.36 (m,
1H), 1.39–1.50 (m, 1H), 1.90–1.96 (m, 2H), 2.43–2.52 (m, 1H), 2.73 (s,
3H, NMe), 3.64 (q, J = 11.0 Hz, 1H), 4.86–4.94 (m, 2H), 5.62–5.73 (m,
1H), 6.29 (d, J = 15.1 Hz, 1H), 6.81–6.88 (dd, J = 15.1, 7.4 Hz, 1H),
7.48–7.58 (m, 3H, Ph), 7.85 ppm (m, 2H); 13CNMR (75 MHz, CDCl 3): d
= 5.2 (u), 7.0 (d), 14.8 (d), 29.4 (u), 29.5 (d), 33.5 (u), 41.5 (d), 74.4 (d),
Chem. Eur. J. 2008, 14, 6510 – 6528
ꢁ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6521

H.-J. Gais et al.
114.6 (u), 128.5 (d), 129.1 (d), 130.2 (d), 132.3 (d), 138.0 (d), 139.5 (u),
148.7 ppm (d); IR (neat): n˜ = 3065 (m), 2951 (w), 2879 (w), 1637 (s),
1451 (m), 1245 (s), 1149 (w), 1011 (w), 911 (m), 865 cmꢁ1 (m); MS (EI,
70 eV): m/z (%): 407 (5) [M+], 378 (47), 352 (50), 195 (44), 115 (100), 87
(65); HRMS (EI, 70 eV): m/z: calcd for C22H37NO2SSi: 407.2314 [M+];
found: 407.2315.
c) A suspension of CuI (244 mg, 1.28 mmol) in Et2O (10 mL) at ꢁ408C
was treated with nBuLi (1.52 mL of 1.60m solution in hexane,
2.43 mmol). After the mixture was stirred for 30 min, it was warmed to
ꢁ158Cand
a solution of the alkenyl sulfoximine ( Z)-1a (135 mg,
0.34 mmol) in Et2O (2 mL) was added. The mixture was warmed within
1.5 h to 08Cand stirring was continued for 1.5 h at this temperature.
Then saturated aqueous NH4Cl/NH3 (10 mL) was added. Extraction with
Et2O gave a mixture of (E)-9aa, (E)-1a and 4b (143 mg) in a ratio of
6:1:6 and 4b. Chromatography (EtOAc/hexane 80:20) gave (E)-9aa
(79 mg, 78%) containing only traces of (Z)-9aa (ꢂ2%). Quenching of
the above mixture with D2O instead of saturated aqueous NH4Cl/NH3
gave [D]-(Z)-9aa with a D content at the a-position of ꢀ98% according
to NMR spectroscopy.
A
fonimidoyl]-but-3-enyloxy}dimethylsilane [(Z)-1c]: Imidazole (200 mg,
4 mmol) and ClSiMe2tBu (3 mmol) were added portionwise at 08Cto a
solution of the hydroxy sulfoximine (Z)-14c (150 mg, 0.4 mmol) in
CH2Cl2 (5 mL). After the mixture was stirred for 10 h at room tempera-
ture, half-saturated aqueous NaHCO3 was added and the mixture was ex-
tracted with CH2Cl2. The combined organic phases were dried (MgSO4)
and concentrated in vacuo. Purification by chromatography (hexane/
EtOAc 80:20) afforded silyl ether (Z)-1c (180 mg, 95%) as a colorless
d) A suspension of CuI (244 mg, 1.28 mmol) in Et2O (10 mL) at ꢁ408C
was treated with nBuLi (1.52 mL of 1.60m solution in hexane,
2.44 mmol). After the mixture was stirred for 1 h, it was treated with a
solution of the alkenyl sulfoximine (Z)-1a (202 mg, 0.51 mmol) in Et2O
(2 mL). The mixture was warmed within 18 h to room temperature. Then
saturated aqueous NH4Cl/NH3 (10 mL) was added. Extraction with Et2O
gave a mixture of (E)-9aa, 15a, 4b and (Z)-6aa. Separation by chroma-
tography first with hexane and then with EtOAc/hexane 50:50 gave a
mixture (83 mg) of (E)-9aa (52% chemical yield) and 15a (3% chemical
yield) (Rf = 0.23) in a ratio of 94:6 and then (Z)-6aa (35 mg, 23%) (Rf =
0.67) as colorless oils.
1
liquid. [a]D = ꢁ80.7 (c= 1.3 in CH2Cl2); H NMR (400 MHz, CDCl3): d
= 0.0 (s, 3H), 0.28 (s, 3H), 0.89 (d, J = 7.9 Hz, 3H), 1.13 (s, 9H), 1.18
(d, J
= 6.6 Hz, 3H), 1.91–2.01 (seq, J = 13.7 Hz, 1H), 2.54 (s, 3H,
NMe), 3.79–3.86 (m, 1H), 5.17 (d, J = 3.6 Hz, 1H), 6.35 (d, J = 11.3 Hz,
1H), 6.53 (t, J = 11.5 Hz, 1H), 7.42–7.55 (m, 5H, Ph), 7.98–8.02 ppm (m,
2H); 13CNMR (100 MHz, CDCl 3): d = ꢁ4.8 (d), ꢁ4.1 (d), 18.3 (u), 20.3
(d), 21.5 (d), 26.0 (d), 28.5 (d), 29.0 (d), 50.9 (d), 75.1 (d), 126.6 (d), 127.0
(d), 127.8 (d), 128.5 (d), 128.8 (d), 131.2 (d), 132.2 (d), 140.5 (u), 143.4
(u), 145.7 ppm (d); IR (neat): n˜ = 2956 (w), 2859 (w), 2802 (s), 1467 (m),
1365 (m), 1253 (w), 1150 (w), 1086 (w), 963 (s), 921 (m), 863 (w),
839 cmꢁ1 (m); MS (EI, 70 eV): m/z (%): 457 (11), 400 (42), 303 (16), 302
(59), 221 (90), 170 (42), 75 (53), 73 (100); HRMS (EI): m/z: calcd for
C26H39NO2SSi: 457.2470 [M+]; found 457.2470.
e) A suspension of CuI (186 mg, 0.98 mmol) in Et2O (10 mL) at ꢁ408C
was treated with nBuLi (1.42 mL of 1.60m solution in hexane,
2.28 mmol). After the mixture was stirred for 30 min, it was warmed to
ꢁ158Cand
a solution of the alkenyl sulfoximine ( Z)-1a (202 mg,
0.51 mmol) in Et2O (2 mL) was added. The mixture was warmed within
18 h to room temperature and saturated aqueous NH4Cl/NH3 (10 mL)
was added. Extraction with Et2O gave a mixture of (E)-9aa, (Z)-9aa and
(Z)-6aa in a ratio of 44:25:31 and 4b. Chromatography first with pentane
and then with EtOAc gave a mixture of (E)-9aa and (Z)-9aa (53 mg,
51%) (Rf = 0.23) in a ratio of 1.7:1 as a colorless oil and then (Z)-6aa
(23 mg, 21%) as a yellow oil.
A
fonimidoyl]-but-3-enyloxy}dimethylsilane [(E)-1c]: nBuLi (2.5 mL of
1.6m solution in hexane, 4 mmol) was added at ꢁ408Cto a solution of
sulfoximine (Z)-1c (150 mg, 0.32 mmol) in Et2O (5 mL). After the mix-
ture was stirred for 10 min, it was allowed to warm to room temperature.
Then half-saturated aqueous NH4Cl was added and the mixture was ex-
tracted with Et2O. The combined organic phases were dried (MgSO4)
and concentrated in vacuo. Purification by chromatography (hexane/
EtOAc 80:20) afforded sulfoximine (E)-1c (140 mg, 93%) as a colorless
f) A suspension of CuI (228 mg, 1.20 mmol) in Et2O (10 mL) at ꢁ408C
was treated with nBuLi (1.7 mL of 1.60m solution in hexane, 2.76 mmol).
After the mixture was stirred for 1 h, it was warmed to ꢁ158Cand treat-
ed with a solution of (E)-1a (138 mg, 0.35 mmol) in Et2O (2 mL). The
mixture was warmed within 3.5 h to 08Cand treated with saturated aque-
ous NH4Cl/NH3 (10 mL). Purification by chromatography (EtOAc/
hexane 80:20) gave (E)-1a (135 mg, 98%).
1
liquid. [a]D = +54.7 (c= 3.4 in CH2Cl2); H NMR (300 MHz, CDCl3): d
= ꢁ0.30 (s, 3H), 0.00 (s, 3H), 1.13 (s, 9H), 0.94 (d, J = 6.7 Hz, 3H), 1.06
(d, J = 6.7 Hz, 3H), 1.85 (seq, J = 13.8 Hz, 1H), 2.05 (sep, J = 10.9 Hz,
1H), 2.77 (s, 3H, NMe), 4.88 (d, J = 4.2 Hz, 1H), 5.95 (d, J = 15.1 Hz,
1H), 6.88 (dd, J = 15.3, 10.4 Hz, 1H), 6.95–6.99 (m, 2H, Ph), 7.02–7.15
(m, 3H, Ph), 7.55–7.68 (m, 3H, Ph), 7.85–7.89 ppm (m, 2H); 13CNMR
(100 MHz, CDCl3): d = ꢁ4.8 (d), ꢁ4.1 (d), 18.3 (u), 20.3 (d), 21.5 (d),
26.0 (d), 28.5 (d), 29.0 (d), 50.9 (d), 75.1 (d), 126.6 (d), 127.0 (d), 127.8
(d), 128.5 (d), 128.8 (d), 131.2 (d), 132.2 (d), 140.5 (u), 143.4 (u),
145.7ppm (d); IR (neat): n˜ = 3028 (s), 2956 (s), 2879 (s), 2802 (s), 1447
(m), 1388 (m), 1247 (s), 1150 (s), 1076 (s), 1044 (s), 874 (s), 807 cmꢁ1 (m);
MS (EI, 70 eV): m/z (%): 457 (11), 400 (42), 303 (16), 302 (59), 221
(100), 115 (42), 75 (23), 73 ppm (13); HMRS (EI): m/z: calcd for
C26H39SSiNO2: 457.2470 [M+]; found 457.2470.
Triethyl (ꢁ)-(E,2S,3R)-3-isopropylnon-4-en-2-yloxy)silane [(E)-9aa]:
[a]D = ꢁ38.3 (c= 0.48 in Et2O); GC: tR = 8.22 (S1) and 10.07 min (S2);
1H NMR (300 MHz, C6D6): d = 0.62 (brq, J = 7.9 Hz, 6H), 0.88 (t, J =
7.1 Hz, 3H), 0.95 (d, J = 6.7 Hz, 3H), 1.00 (d, J = 6.7 Hz, 3H), 1.03 (t,
J = 7.9 Hz, 9H), 1.14 (d, J = 6.4 Hz, 3H), 1.33 (m, 4H), 1.48 (ddd, J =
9.6, 7.7, 3.2 Hz, 1H), 1.87 (m, 1H), 2.05 (brq, J = 6.7 Hz, 2H), 4.03 (qd,
J = 6.2, 3.2 Hz, 1H), 5.36 (dt, J = 15.4, 6.6 Hz, 1H), 5.51 ppm (ddt, J =
15.4, 9.7, 1.2 Hz, 1H); 13CNMR (75 MHz, C 6D6): d = 5.7 (u), 7.3 (d),
14.1 (d), 21.2 (d), 21.8 (d), 23.3 (d), 22.6 (u), 28.7 (d), 32.3 (u), 32.9 (u),
58.4 (d), 69.1 (d), 129.6 (d), 133.2 ppm (d); GC-MS (EI, 70 eV): m/z (%):
299 [M+] (2), 270 (23), 269 (100), 160 (11), 159 (85), 131 (Et3SiO, 69),
115 (Et3Si, 40), 111 (15), 103 (16), 97 (20), 75 (10), 69 (13); IR (CH2Cl2):
n˜ = 2957 (vs), 2927 (vs), 2876 (vs), 2732 (w), 1734 (w), 1459 (m), 1416
(m), 1371 (m), 1323 (w), 1260 (m), 1239 (m), 1163 (m), 1130 (m), 1071
(s), 1007 (s), 977 (m), 943 (m), 892 (w), 805 cmꢁ1 (w); elemental analysis
calcd (%) for C18H38OSi (298.58): C72.41, H 12.83; found: C72.08, H
12.64; HMRS (EI, 70 eV): m/z: calcd for C18H38OSi: 269.2300 [M+
ꢁC2H5]; found 269.2300.
Reactions of( Z)-1a und (E)-1a with LiCuBu2 and LiCuBu2/LiBu
a) A suspension of CuI (195 mg, 1.03 mmol) in Et2O (10 mL) at ꢁ408C
was treated with nBuLi (1.22 mL of 1.60m solution in hexane,
1.95 mmol). After the mixture was stirred for 1 h, it was treated with a
solution of the alkenyl sulfoximine (Z)-1a (76 mg, 0.19 mmol) in Et2O
(1 mL). Then the mixture was stirred for 1 h at ꢁ408Cand D O (0.1 mL)
2
was added. Purification by chromatography (EtOAc/hexane 80:20) gave
(Z)-1a (190 mg, 97%) containing no D atom (ꢂ 3%) at the a-position.
b) A suspension of CuI (268 mg, 1.41 mmol) in Et2O (10 mL) at ꢁ408C
was treated with nBuLi (1.60 mL of 1.60m solution hexane, 2.56 mmol).
After the mixture was stirred for 30 min, it was treated with a solution of
the alkenyl sulfoximine (Z)-1a (73 mg, 0.18 mmol) in Et2O (2 mL). Then
the mixture was warmed within 3 h to 08C, stirred for 1 h at this tempera-
ture and treated with saturated aqueous NH4Cl/NH3 (10 mL). Purifica-
tion by chromatography (EtOAc/hexane 80:20) gave a mixture (28 mg)
of (E)-9aa (47% chemical yield) and 15 (4% chemical yield) (Rf = 0.78)
in a ratio of 93:7 and sulfoximine (Z)-1a (19 mg, 26%) as colorless oils.
Triethyl (ꢁ)-(Z,2S,3R)-3-isopropylnon-4-en-2-yloxy)silane [(Z)-9aa]:
GC: tR = 8.42 min (S1); GC-MS (EI, 70 eV): m/z (%): 270 [M+ꢁC2H5]
(19), 269 (100), 160 (7), 159 (48), 131 (20), 115 (11), 111 (11), 103 (6), 97
(11), 69 (6), 55 (4).
Triethyl (2S,3R)-3-isopropylpent-4-en-2-yloxy)silane (15): GC :tR =
7.89 min (S2); 1H NMR (300 MHz, CDCl3, in part): d = 4.85 (dd, J =
17.4, 2.4 Hz, 1H), 5.01 (dd, J = 10.2, 2.4 Hz, 1H), 5.61 ppm (dt, J =
17.4, 10.2 Hz, 1H); GC-MS (EI, 70 eV): m/z (%): 243 [M+] (1), 241 (2),
6522
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ꢁ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 6510 – 6528

Sulfoximines Reactions
FULL PAPER
214 (16), 213 (100), 160 (5), 159 (30), 131 (8), 115 (5), 111 (5), 103 (3), 69
(8), 59 (2), 55 (2).
5.29 (u), 6.96 (d), 13.43 (d), 20.18 (d), 21.45 (d), 22.46 (d), 28.72 (d), 50.90
(d), 68.88 (d), 125.06 (d), 130.25 ppm (d).
A
Triethyl (1S,2R)-3-isopropyl-5-methylhex-4-en-2-yloxy)silane (16a): GC :
tR = 8.58 min (S2); GC-MS (EI, 70 eV): m/z (%): 269 [M+ꢁ2] (1), 243
(4), 242 (17), 241 (100), 240 (3), 185 (2), 160 (3), 159 (30), 131 (19), 115
(13), 103 (7), 83 (22), 81 (8), 69 (14).
11.60 min (S2); 1H NMR (300 MHz, C6D6): d = 0.75 (brq, J = 7.9 Hz,
6H), 0.87 (d, J = 6.9 Hz, 3H), 0.91 (t, J = 7.2 Hz, 3H), 0.97 (d, J =
6.9 Hz, 3H), 1.01 (t, J = 8.0 Hz, 9H), 1.17 (d, J = 6.2 Hz, 3H), 1.25–1.47
(m, 6H), 1.79 (m, 1H), 1.99–2.12 (m, 2H), 3.72 (q, J = 6.0 Hz, 1H),
6.04 ppm (brd, J = 11.1 Hz, 1H); 13CNMR (75 MHz, C 6D6): d = 4.9
(u), 8.0 (d), 14.2 (d), 19.1 (d), 21.5 (d), 2.0 (d), 23.3 (u), 2.90 (d), 4.0, 38.0
(u), 54.2 (d), 67.7 (d), 142.0 (d), 142.9 ppm (u); GC-MS (EI, 70 eV): m/z
(%): 297 [M+ꢁ2] (3), 269 (11), 203 (33), 191 (17), 165 (69), 161 (28), 159
(7), 149 (9), 145 (14), 138 (22), 123 (9), 117 (17), 115 (75), 114 (10), 111
(41), 109 (16), 104 (10), 103 (90), 97 (49), 95 (20), 89 (100), 85 (12), 83
(17), 81 (13), 69 (28), 61 (17), 59 (10).
Reactions of( Z)-1a and (E)-1a with LiCuPh2 and LiCuPh2/LiPh
a) A suspension of CuI (148 mg, 0.78 mmol) in Et2O (15 mL) at ꢁ408C
was treated with PhLi (0.80 mL of 1.80m solution in cyclohexane/Et2O,
1.44 mmol). After the mixture was stirred for 1 h, a solution of (Z)-1a
(74 mg, 0.19 mmol) in Et2O (2 mL) was added and the mixture was
warmed within 18 h to room temperature. Then saturated aqueous
NH4Cl/NH3 (10 mL) was added. Purification by chromatography
(hexane/EtOAc 80:20) gave a mixture of 4b, (E)-9ac (85% chemical
yield), (Z)-9ac (2% chemical yield) and (E,E)-17aa (2% chemical
yield).
Reactions of( Z)-1a and (E)-1a with LiCuMe2 and LiCuMe2/LiMe
a) A suspension of CuI (259 mg, 1.36 mmol) in Et2O (10 mL) at ꢁ408C
was treated with MeLi (1.62 mL of 1.60m solution in Et2O, 2.59 mmol).
After the mixture was stirred for 1 h, a solution of (Z)-1a (202 mg,
0.51 mmol) in Et2O (2 mL) was added. The mixture was warmed within
18 h to room temperature and saturated aqueous NH4Cl/NH3 (10 mL)
was added. Purification by chromatography (EtOAc/hexane 50:50) gave
a mixture (105 mg) of (E)-9ab (75% chemical yield), (Z)-9ab (2%
chemical yield) and 16ab (2% chemical yield) (Rf = 0.75) in a ratio of
30:1:1 as a colorless oil.
b) A suspension of CuI (559 mg, 2.94 mmol) in Et2O (15 mL) at ꢁ408C
was treated with PhLi (3.80 mL of 1.80m solution in cyclohexane/Et2O,
6.83 mmol). After the mixture was stirred for 30 min, it was warmed to
ꢁ158Cand a solution of ( Z)-1a (400 mg, 1.01 mmol) in Et2O (5 mL) was
added. The mixture was warmed within 1.5 h to 08Cand stirring was con-
tinued for 3.5 h at this temperature. Then saturated aqueous NH4Cl/NH3
(10 mL) was added. Purification by chromatography (cyclohexane/
EtOAc 91:9) gave (Z)-6ac (239 mg, 74%) (Rf = 0.31) as a colorless oil.
In addition a mixture of (E)-9ac, (Z)-9ac and (E,E)-17aa (150 mg) was
obtained.
b) A suspension of CuI (325 mg, 1.71 mmol) in Et2O (10 mL) at ꢁ408C
was treated with MeLi (2.00 mL of 1.60m solution in Et2O, 3.20 mmol).
After the mixture was stirred for 1 h, a solution of (Z)-1a (145 mg,
0.37 mmol) in Et2O (2 mL) was added. The mixture was warmed within
18 h to room temperature and treated with D2O (0.1 mL). Work-up gave
a mixture (144 mg) of [D]-(E)-9ab (D content at the a-position ꢀ98%),
4b and [D]-(E)-1a (D content at the a-position ꢀ98%) in a ratio of
15:17:1. Purification by chromatography (EtOAc/hexane 80:20) (Rf =
0.77) gave a mixture (73 mg) of [D]-(E)-9ab (71% chemical yield) [D]-
(E)-9ab (3% chemical yield) and 16a (2% chemical yield).
c) A suspension of CuI (144 mg, 0.76 mmol) in Et2O (10 mL) at ꢁ408C
was treated with PhLi (1.10 mL of 1.80m solution in cyclohexane/Et2O,
1.98 mmol). After the mixture was stirred for 1 h, it was warmed to
ꢁ158Cand a solution of ( E)-1a (188 mg, 0.48 mmol) in Et2O (2 mL) was
added. The mixture was warmed within 1.5 h to 08Cand stirring was con-
tinued for 2 h at this temperature. Then saturated aqueous NH4Cl/NH3
(10 mL) was added. Purification by chromatography afforded a mixture
of 4b, (Z)-9ac (60% chemical yield), (E)-9ac (4% chemical yield) and
(Z,Z)-17aa (30% chemical yield). Further purification by chromatogra-
phy (hexane/EtOAc 80:20) gave a mixture (64 mg) of (Z)-9ac (22%
chemical yield) and (Z,Z)-17aa (11% chemical yield) (Rf = 0.81) in a
ratio of 2:1. In addition a mixture (56 mg) of (E)-9ac, (Z)-9ac and (Z,Z)-
17aa containing biphenyl was obtained. A separation could only be ach-
ieved after desilylation of the mixture of (E)-9ac, (Z)-9ac und (Z,Z)-
17aa at the stage of the corresponding alcohols (see Scheme 13).
c) A suspension of CuI (252 mg, 1.32 mmol) in Et2O (10 mL) at ꢁ408C
was treated with MeLi (1.90 mL of 1.60m solution in Et2O, 3.04 mmol).
After the mixture was stirred for 1 h, it was warmed to ꢁ158Cand a so-
lution of (Z)-1a (151 mg, 0.38 mmol) in Et2O (2 mL) was added. The
mixture was warmed within 1.5 h to 08Cand stirring was continued for
1.5 h at this temperature. Then saturated aqueous NH4Cl/NH3 (10 mL)
was added. Extraction with Et2O gave a mixture of (E)-9ab and (Z)-9ab
in a ratio of 2.3:1 and sulfoximine (E)-1a (5%). Purification by chroma-
tography (hexane/EtOAc 80:20) gave a mixture (50 mg) of (E)-9ab
(38% chemical yield), (Z)-9ab (12% chemical yield) and 16a (1%)
(Rf = 0.73).
Triethyl (ꢁ)-(Z,2S,3R)-3-(isopropyl)-5-phenyl-5-(triethylsilyl)pent-4-en-2-
ol [(Z)-6ac]: [a]D = ꢁ43.8 (c= 0.79 in Et2O); GC: tR = 10.88 min (S1);
1H NMR (500 MHz, CDCl3): d = 0.66 (brq, J = 7.9 Hz, 6H), 0.92 (t, J
= 7.9 Hz, 9H), 0.92 (d, J = 6.9 Hz, 3H), 1.03 (d, J = 6.8 Hz, 3H), 1.26
(d, J = 6.3 Hz, 3H), 1.62 (brs, 1H), 1.90 (o, J = 6.7 Hz, 1H), 2.16 (dt, J
= 11.4, 6.0 Hz, 1H), 3.84 (q, J = 6.2 Hz, 1H), 6.05 (d, J = 11.4 Hz, 1H),
7.05 (m, 2H), 7.17 (tt, J = 7.4, 1.3 Hz, 1H), 7.25 ppm (brt, J = 7.4 Hz,
2H); 13CNMR (75 MHz, CDCl 3): d = 4.3 (u), 7.6 (d), 18.9 (d), 21.1 (d),
21.8 (d), 28.8 (d), 54.0 (d), 68.0 (d), 125.5 (d), 127.6 (d), 127.8 (d), 146.3
(d), 146.5, 147.9 ppm (u); MS (EI, 70 eV): m/z (%): 290 [M+ꢁEt] (5),
289 (7), 274 (19), 271 (12), 246 (10), 245 (34), 243 (13), 215 (14), 201 (11),
173 (12), 163 (14), 159 (13), 158 (22), 145 (13), 135 (16), 131 (12), 116
(12), 115 (Et3Si, 100), 107 (11), 105 (12), 103 (87), 87 (61), 75 (40); IR
(capillary): n˜ = 3399 (m, br), 3075 (w), 3055 (w), 3014 (w), 2956 (vs),
2934 (s), 2910 (s), 2874 (vs), 2731 (w), 1939 (w), 1866 (w), 1799 (w), 1744
(w), 1596 (m), 1489 (m), 1461 (s), 1441 (s), 1419 (s), 1385 (m), 1367 (m),
1351 (w), 1319 (w), 1238 (m), 1207 (w), 1156 (m), 1138 (w), 1106 (w),
1072 (w), 1043 (m), 1031 (w), 1002 (s), 971 (w), 912 (m), 878 (w), 838
(w), 813 cmꢁ1 (m); elemental analysis calcd (%) for C20H34OSi (318.57):
C75.40, H 10.76; found: C75.19, H 11.02.
Triethyl (ꢁ)-(E,2S,3R)-3-isopropylhex-4-en-2-yloxy)silane [(E)-9ab]:
[a]D = ꢁ33.0 (c= 0.55 in n-hexane); GC: tR = 5.50 (S1) and 8.21 min
(S2); 1H NMR (300 MHz, C6D6): d = 0.61 (brq, J = 7.9 Hz, 6H), 0.93
(d, J = 6.7 Hz, 3H), 0.99 (d, J = 7.0 Hz, 3H), 1.03 (t, J = 8.0 Hz, 9H),
1.13 (d, J = 6.2 Hz, 3H), 1.49 (ddd, J = 9.7, 7.7, 3.4 Hz, 1H), 1.65 (dd, J
= 6.2, 1.6 Hz, 3H), 1.84 (m, 1H), 3.99 (qd, J = 6.2, 3.4 Hz, 1H), 5.34
(dq, J = 15.2, 6.2 Hz, 1H), 5.51 ppm (ddq, J = 15.2, 9.5, 1.6 Hz, 1H);
13CNMR (75 MHz, C 6D6): d = 5.7 (u), 7.3 (d), 18.2 (d), 20.9 (d), 21.8
(d), 23.0 (d), 28.7 (d), 58.3 (d), 69.1 (d), 127.4 (d), 130.8 ppm (d); GC-MS
(EI, 70 eV): m/z (%): 256 [M+] (1), 255 (2), 228 (16), 227 (100), 159 (36),
131 (17), 115 (12), 103 (6), 69 (21); IR (capillary): n˜ = 2956 (vs), 2930
(vs), 2876 (vs), 2731 (w), 1727 (w), 1667 (w), 1602 (w), 1458 (s), 1416
(m), 1376 (m), 1320 (w), 1239 (m), 1164 (m), 1149 (m), 1129 (m), 1073
(s), 1016 (s), 975 (m), 945 (m), 918 (w), 891 (w), 876 (w), 842 cmꢁ1 (w);
elemental analysis calcd (%) for C15H32OSi (256.50): C70.24, H 12.57;
found: C70.05, H 12.79; HMRS (EI, 70 eV): m/z: calcd for C15H32OSi:
227.1831 [M+ꢁC2H5], found: 227.1830.
Triethyl (E,2S,3R)-3-isopropyl-5-phenylpent-4-en-2-yloxy)silane [(E)-
1
Triethyl (ꢁ)-(E,2S,3R)-3-isopropylhex-4-en-2-yloxy)silane [(Z)-9ab]:
9ac]: GC :tR = 10.53 min (S1); H NMR (300 MHz, CDCl3, in part): d =
GC: tR = 8.42 min (S2); H NMR (300 MHz, CDCl3): d = 0.57 (brq, J =
0.86 (d, J = 6.7 Hz, 3H), 1.13 (d, J = 6.2 Hz, 3H), 1.70 (ddd, J = 9.5,
7.4, 3.7 Hz, 1H), 1.86 (m, 1H), 4.07 (qd, J = 6.2, 3.7 Hz, 1H), 6.16 (dd, J
= 15.9, 9.4 Hz, 1H), 6.30 ppm (d, J = 15.9 Hz, 1H); 13CNMR (75 MHz,
CDCl3): d = 5.3 (u), 7.0 (d), 20.5 (d), 21.6 (d), 22.9 (d), 28.6 (d), 58.4 (d),
68.8 ppm (d); GC-MS (EI, 70 eV): m/z (%): 294 (2), 293 (7), 292 (32),
7.9 Hz, 6H), 0.81 (d, J
6.4 Hz, 3H), 1.58 (dd, J = 6.7, 2.0 Hz, 3H), 1.72 (m, 1H), 1.94 (ddd, J =
10.4, 7.7, 3.7 Hz, 1H), 4.00 (qd, J = 6.0, 3.7 Hz, 1H), 5.30 (m, 1H),
5.61 ppm (dq, J = 11.4, 6.7 Hz, 1H); 13C NMR (75 MHz, CDCl3): d =
Chem. Eur. J. 2008, 14, 6510 – 6528
ꢁ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6523

H.-J. Gais et al.
221 (10), 205 (17), 189 (10), 179 (11), 161 (28), 133 (36), 131 (19), 129
(10), 118 (14), 116 (22), 104 (6), 90 (26).
(7E,9E,5S,6R,11S,12S)-3,3,14,14-Tetraethyl-5,11-disopropyl-5,12-dimeth-
ly-8-phenyl-4,13-dioxa-3,14-disilahexadeca-7,9-diene [(E,E)-17aa]: GC
tR = 16.50 min (S1); 1H NMR (300 MHz, CDCl3): d = 0.50 (brq, J =
7.9 Hz, 6H), 0.57 (brq, J = 7.9 Hz, 6H), 0.75 (d, J = 6.7 Hz, 3H), 0.88
(d, J = 6.7 Hz, 3H), 0.88 (t, J = 7.9 Hz, 9H), 0.91 (m, 3H), 0.94 (t, J =
7.9 Hz, 9H), 0.99 (d, J = 6.7 Hz, 3H), 1.10 (d, J = 6.1 Hz, 3H), 1.13 (d,
J = 6.1 Hz, 3H), 1.61 (ddd, J = 9.6, 7.4, 3.7 Hz, 1H), 1.70 (o, J =
6.7 Hz, 1H), 1.84 (o, J = 6.7 Hz, 1H), 2.21 (ddd, J = 10.8, 8.0, 3.4 Hz,
1H), 3.97 (qd, J = 6.1, 3.7 Hz, 1H), 4.09 (qd, J = 6.1, 3.4 Hz, 1H), 5.40
(dd, J = 15.8, 9.6 Hz, 1H), 5.42 (d, J = 10.8 Hz, 1H), 6.35 (d, J =
15.8 Hz, 1H), 7.20–7.34 ppm (m, 5H); 13CNMR (75 MHz, CDCl 3): d =
5.27 (u), 5.31 (u), 6.9 (d), 7.0 (d), 20.5 (d), 20.7 (d), 21.5 (d), 21.6 (d), 22.7
(d), 22.9 (d), 28.5, 29.1 (d), 51.9 (d), 58.8 (d), 68.9 (d), 69.1 (d), 127.7 (d),
128.9 (d), 126.4 (d), 129.7 (d), 130.8 (d), 133.9 (d), 141.3 (d), 143.6 ppm
(u); GC-MS (EI, 70 eV): m/z (%): 427 [M+ꢁC2H6] (1), 373 (1), 271 (1),
270 (2), 221 (6), 205 (19), 163 (8), 162 (14), 161 (100), 159 (11), 133 (29),
131 (9).
:
Triethyl (Z,2S,3R)-3-isopropyl-5-phenylpent-4-en-2-yloxy)silane [(Z)-
1
9ac]: GC :tR = 10.36 min (S1); H NMR (500 MHz, CDCl3, in part): d =
0.58 (m, 6H), 0.87 (d, J = 6.7 Hz, 3H), 0.96 (m, 9H), 1.0 (m, 3H), 1.10
(d, J = 6.1 Hz, 3H), 1.78 (o, J = 6.7 Hz, 1H), 2.31 (ddd, J = 11.1, 7.3,
4.0 Hz, 1H), 4.00 (qd, J = 6.1, 4.0 Hz, 1H), 5.35 (t, J = 11.6 Hz, 1H),
6.63 (d, J = 12.0 Hz, 1H), 7.14–7.32 ppm (m, 5H); 13CNMR (75 MHz,
CDCl3): d = 5.3 (u), 7.1 (d), 20.1 (d), 21.2 (d), 22.7 (d), 28.8 (d), 51.1 (d),
68.9 (d), 128.0 (d), 128.8 ppm (d); GC-MS (EI, 70 eV): m/z (%): 293 (2),
292 (10), 221 (6), 205 (10), 189 (4), 179 (8), 161 (16), 132 (21), 131 (7),
129 (5), 118 (6), 116 (13), 104 (3), 90 (36).
(7Z,9Z,5S,6R,11S,12S)-3,3,14,14-Tetraethyl-6,11-diisopropylmethyl-5,12-
dimethy-8-phenyl-4,13-dioxa-3,14-disilahexadeca-7,9-diene [(Z,Z)-17aa]:
1H NMR (300 MHz, CDCl3, in part): d = 0.58 (m, 12H), 0.78 (d, J =
6.4 Hz, 3H), 0.80 (d, J = 6.4 Hz, 3H), 0.86 (d, J = 6.0 Hz, 3H), 0.96 (m,
18H), 1.0 (m, 3H), 1.02 (d, J = 6.1 Hz, 3H), 1.03 (d, J = 6.1 Hz, 3H),
1.57–1.79 (m, 4H), 3.35 (m, 2H), 5.35 (t, J = 11.6 Hz, 1H), 5.70 (d, J =
10.1 Hz, 1H), 6.26 (d,
J = 12.1 Hz, 1H), 7.14–7.32 ppm (m, 5H);
13CNMR (75 MHz, CDCl 3): d = 20.9 (d), 21.2 (d), 21.5 (d), 22.9 (d), 23.3
(d), 28.9 (d), 29.0 (d), 50.3 (d), 51.9 (d), 68.4 (d), 69.1 ppm (d).
Scheme 13. Desilylation of silyl ethers (E)-9ac, (Z)-9ac, (E,E)-17aa and
(Z,Z)-17aa.
Desilylation ofthe mixture of(
(Scheme 13)
E)-9ac, (Z)-9ac and (E,E)-17aa
a) A solution of a mixture of (E)-9ac, (Z)-9ac und (E,E)-17aa (150 mg)
in THF (10 mL) at 08Cwas treated with Bu 4NF (78 mg, 0.30 mmol).
After the mixture was stirred for 60 h at room temperature, the solvent
was removed in vacuo. Purification by chromatography (hexane/EtOAc
80:20) gave a mixture of alcohols (E)-33 and (Z)-33 (22 mg, 11% based
on (Z)-1a) in a ratio of 4.8:1 and diol (E,E)-34 (6 mg, 4% based on (Z)-
1a) (Rf = 0.16).
(4E,6E,2S,3R,8SR,9S)-3,8-Diisopropyl-5-phenyldeca-4,6-diene-2,9-diol
[(E,E)-34]: 1H NMR (500 MHz, C6D6): d = 0.75 (d, J = 6.7 Hz, 3H),
0.89 (d, J = 6.6 Hz, 3H), 0.90 (d, J = 6.8 Hz, 3H), 0.99 (d, J = 6.6 Hz,
3H), 1.03 (d, J = 6.2 Hz, 3H), 1.12 (d, J = 6.2 Hz, 3H), 1.62 (dddd, J =
9.7, 6.6, 5.2, 1.2 Hz, 1H), 1.68 (o, J = 6.6 Hz, 1H), 1.85 (o, J = 6.8 Hz,
1H), 2.31 (ddd, J = 10.9, 7.0, 4.8 Hz, 1H), 3.63 (q, J = 5.8 Hz, 1H), 3.81
(qu, J = 5.9 Hz, 1H), 5.52 (d, J = 11.0 Hz, 1H), 5.65 (ddd, J = 15.6, 9.7,
1.2 Hz, 1H), 6.59 (d, J = 15.6 Hz, 1H), 7.11 (tt, J = 7.3, 1.3 Hz, 1H),
7.19 (t, J = 7.5 Hz, 2H), 7.41 ppm (dd, J = 8.0, 1.4 Hz, 2H); 13CNMR
(75 MHz, CDCl3): d = 18.8 (d), 19.0 (d), 21.4 (d), 21.5 (d), 21.7 (d), 22.0
(d), 28.5 (d), 29.5 (d), 51.6 (d), 58.4 (d), 67.8 (d), 68.6 (d), 128.1 (d), 128.8
(d), 127.2 (d), 129.5 (d), 131.8 (d), 132.9 (d), 142.7 (u), 143.6 ppm (u).
A
=
8.16 min (S1); 1H NMR (300 MHz, CDCl3): d = 0.90 (d, J = 6.7 Hz,
3H), 0.96 (d, J = 6.7 Hz, 3H), 1.22 (d, J = 6.1 Hz, 3H), 1.58 (brs, 1H),
1.85 (m, 1H), 1.90 (m, 1H), 3.93 (q, J = 6.1 Hz, 1H), 6.13 (dd, J = 15.8,
9.7 Hz, 1H), 6.44 (d, J = 15.8 Hz, 1H), 7.22 (m, 1H), 7.31 (m, 2H),
7.39 ppm (m, 2H); 13C NMR (75 MHz, CDCl3): d = 18.86 (d), 21.5 (d),
21.9 (d), 28.7 (d), 58.0 (d), 68.0 (d), 126.3 (d), 128.6 (d), 127.4 (d), 128.1
(s), 134.4 (d), 137.4 (u); GC-MS (EI, 70 eV): m/z (%): 160 (6), 145 (2),
131 (2), 128 (3), 117 (18), 104 (10), 89 (37), 77 (1), 61 ppm (10).
Desilylation ofthe mixture of( E)-9ac, (Z)-9ac and (Z,Z)-17aa: A solu-
tion of a mixture (E)-9ac, (Z)-9ac and (Z,Z)-17aa (120 mg) in THF
(10 mL) at 08Cwas treated with Bu 4NF (50 mg, 0.19 mmol). After the
mixture was stirred for 18 h at room temperature, the solvent was re-
moved in vacuo. Purification by chromatography (hexane/EtOAc 80:20)
gave a mixture of alcohols (E)-33 and (Z)-33 (24 mg, 25% based on (Z)-
1a) (Rf = 0.31) in a ratio of 3:16 and diol (Z,E)-34 (16 mg, 20% based
on (Z)-1a) (Rf = 0.17).
A
=
7.66 min (S1); 1H NMR (300 MHz, CDCl3): d = 0.89 (d, J = 6.7 Hz,
3H), 0.89 (d, J = 6.9 Hz, 3H), 1.17 (d, J = 6.1 Hz, 3H), 1.49 (brs, 1H),
1.83 (o, J = 6.8 Hz, 1H), 2.45 (dt, J = 11.4, 6.0 Hz, 1H), 3.90 (q, J =
6.1 Hz, 1H), 5.61 (t, J = 11.7 Hz, 1H), 6.78 (d, J = 11.9 Hz, 1H), 7.22–
7.31 ppm (m, 5H); 13C NMR (75 MHz, CDCl3): d = 18.6 (d), 21.4 (d),
21.5 (d), 29.0 (d), 50.7 (d), 68.4 (d), 128.2 (d), 128.7, (d), 126.7 (d), 130.5
(d), 133.7 (d), 137.7 ppm (u); GC-MS (EI, 70 eV): m/z (%): 161 [M+
ꢁC3H7] (1), 160 (4), 131 (2), 129 (2), 128 (2), 117 (15), 104 (9), 89 (45),
77 (1), 61 (12), 45 (11), 43 (100), 42 (12), 32 (9).
(4Z,6Z,2S,3R,8S,9S)-3,8-Diisopropyl-5-phenyl-deca-4,6-diene-2,9-diol
[(Z,E)-34]: GC :tR = 11.79 min (S1); 1H NMR (500 MHz, C6D6): d =
0.78 (d, J = 6.9 Hz, 3H), 0.79 (d, J = 6.7 Hz, 3H), 0.84 (d, J = 6.7 Hz,
3H), 0.88 (d, J = 6.7 Hz, 3H), 1.04 (d, J = 6.2 Hz, 3H), 1.10 (d, J =
6.2 Hz, 3H), 1.33 (brs, 1H), 1.40 (brs, 1H), 1.63–1.90 (m, 4H), 3.66 (brq,
J = 6.1 Hz, 1H), 3.85 (brq, J = 6.1 Hz, 1H), 5.32 (t, J = 11.8 Hz, 1H),
6524
www.chemeurj.org
ꢁ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 6510 – 6528

Sulfoximines Reactions
FULL PAPER
5.75 (d, J = 10.7 Hz, 1H), 6.46 (d, J = 11.8 Hz, 1H), 7.18 (m, 2H), 7.27–
7.35 ppm (m, 3H); 13C NMR (75 MHz, CDCl3): d = 18.5 (d), 19.3 (d),
21.4 (d), 21.6 (d), 21.7 (d), 21.7 (d), 28.8 (d), 29.2 (d), 50.0 (d), 51.5 (d),
68.4 (d), 68.5 (d), 128.1 (d), 129.8 (d), 126.8 (d), 128.8 (d), 131.4 (d), 136.5
(d), 140.4 (u), 142.7 ppm (u).
b) A suspension of CuI (140 mg, 0.73 mmol) in Et2O (5 mL) at ꢁ408C
was treated with MeLi (0.6 mL of 5% solution in Et2O, 1.34 mmol).
After the yellow mixture was stirred for 1 h, a solution of the alkenyl sul-
foximine (Z)-1b (100 mg, 0.24 mmol) in Et2O (2 mL) was added. The
mixture was stirred for 1 h at ꢁ408Cand then allowed to warm room
temperature and stirred for 10 h. The mixture was quenched with aque-
ous NH4Cl and extracted with Et2O. The combined organic phases were
dried (MgSO4) and concentrated in vacuo. GC-MS analysis showed the
formation of (E)-9b, 16b and 5% of (Z,E)-17b. Purification by chroma-
tography (hexane) yielded alkene (E)-9b along with the dimethyl alkene
16b (49 mg) in a ratio of 9:1 as a colorless liquid. Separation by HPLC
(pentane) gave (E)-9b (42 mg, 64%) and 16b (5 mg, 8%) as colorless
liquids.
Reaction of( Z)-1a and (E)-1a with LiCu(CH=CH2)2: A suspension of
A
CuI (282 mg, 1.48 mmol) in Et2O (80 mL) at ꢁ408Cwas treated with vi-
nyllithium (approximately 70 mg, 2 mmol) in Et2O (10 mL). After the
mixture was stirred for 1 h, it was warmed to ꢁ158Cand a solution of
(Z)-1a (156 mg, 0.39 mmol) in Et2O (2 mL) was added. The mixture was
warmed within 1.5 h to 08Cand stirring was continued at this tempera-
ture for 2.5 h. Then saturated aqueous NH4Cl/NH3 was added. Purifica-
tion by chromatography (hexane/EtOAc 80:20) (Rf = 0.69) gave a mix-
ture (75 mg) of (E)-9ad (66% chemical yield), (Z)-9ad (3% chemical
yield) and (Z,E)-17ab (1% chemical yield) in a ratio of 94:4:2 as a color-
less oil.
Triethyl [(5S,6R,E)-6-methylnona-1,7-dien-5-yloxy]silane [(E)-9b]: [a]D
= +15.0 (c= 0.7 in CH2Cl2); 1H NMR (300 MHz, CDCl3): d = 0.50–
0.57 (m, 6H), 0.87 (d, J = 6.9 Hz, 3H), 0.89 (t, J = 7.7 Hz, 9H), 1.35–
1.32 (m, 2H), 1.59 (d, J = 5.8 Hz, 3H), 1.88–1.98 (m, 1H), 2.01–2.11 (m,
1H), 2.13–2.22 (m, 1H), 3.45 (m, 1H), 4.84–4.96 (m, 2H), 5.36–5.51 (m,
2H), 5.77–5.88 ppm (m, 1H); 13CNMR (75 MHz, CDCl 3): d = 5.0, (u),
7.1 (d), 15.4 (d), 18.2 (d), 30.2 (u), 32.6 (u), 42.4 (d), 75.7 (d), 114.0 (u),
124.7 (d), 133.5 (d), 139.0 ppm (d); IR (neat): n˜ = 3075 (m), 2955 (w),
2880 (w), 1640 (m), 1454 (s), 1238 (s), 1080 (w), 1012 (w), 970 (s),
825 cmꢁ1 (s); MS (EI, 70 eV): m/z (%): 199 (100), 143 (6), 115 (38), 87
(22); HRMS (EI, 70 eV): m/z: calcd for C11H23OSi: 199.1518 [M+
ꢁC5H9]; found: 199.1519.
Triethyl (ꢁ)-(E,2S,3R)-3-isopropylhept-4,6-dien-2-yloxy)silane [(E)-9ad]:
[a]D = ꢁ75.8 (c= 1.04 in Et2O); GC: tR
=
7.23 min (S1); 1H NMR
(400 MHz, CDCl3): d = 0.57 (brq, J = 7.9 Hz, 6H), 0.80 (d, J = 6.7 Hz,
3H), 0.91 (d, J = 6.7 Hz, 3H), 0.95 (t, J = 7.9 Hz, 9H), 1.09 (d, J =
6.2 Hz, 3H), 1.57 (ddd, J = 10.0, 7.2, 4.0 Hz, 1H), 1.77 (o, J = 6.8 Hz,
1H), 3.99 (qd, J = 6.2, 4.0 Hz, 1H), 4.95 (dd, J = 10.0, 1.7 Hz, 1H), 5.07
(dd, J = 16.8, 1.7 Hz, 1H), 5.61 (dd, J = 15.2, 10.0 Hz, 1H), 5.98 (dd, J
= 15.2, 10.2 Hz, 1H), 6.35ppm (dt, J = 16.8, 10.1 Hz, 1H); 13CNMR
(100 MHz, CDCl3): d = 5.2 (u), 6.9 (d), 20.2 (d), 21.6 (d), 22.8 (d), 28.4
(d), 57.9 (d), 68.7 (d), 114.3 (u), 133.4 (d), 134.6 (d), 137.5 ppm (d); GC-
MS (EI, 70 eV): m/z (%): 268 [M+] (1), 267 (5), 253 (2), 241 (4), 240
(16), 239 [M+ꢁC2H5] (97), 219 (12), 204 (12), 203 (78), 195 (10), 159
(100), 157 (15), 155 (9), 137 (24), 131 (Et3SiO, 12), 115 (Et3Si, 3), 103 (5),
95 (8), 81 (14); IR (capillary): n˜ = 3086 (w), 3037 (w), 2957 (vs), 2911 (s),
2877 (vs), 2733 (w), 1796 (w), 1651 (w), 1603 (w), 1460 (m), 1415 (m),
1383 (m), 1372 (m), 1357 (m), 1323 (w), 1264 (w), 1239 (m), 1159 (s),
1129 (s), 1109 (s), 1070 (s), 1005 (vs), 958 (s), 939 (m), 895 (s), 852 (w),
A
:
tR = 9.58 min; [a]D = +5.2 (c= 0.6 in CH2Cl2); 1H NMR (300 MHz,
CDCl3): d = 0.52–0.57 (m, 6H), 0.85 (d, J = 6.9 Hz, 3H), 0.89 (m, 9H),
1.35–1.42 (m, 2H), 1.54 (d, J = 1.5 Hz, 3H), 1.62 (d, J = 1.2 Hz, 3H),
1.86–1.99 (m, 1H), 1.99–2.14 (m, 1H), 2.34–2.46 (m, 1H), 3.46 (dq, J =
9.9, 3.71, 1H), 4.84–4.94 (m, 2H), 4.96 (m, 1H), 5.68–5.82 ppm (m, 1H);
IR (neat): n˜ = 2927 (w), 2875 (s), 1637 (s), 1458 (m), 1216 (s), 1156 (m),
1011 (m), 912 (m), 759 cmꢁ1 (w); GC-MS (EI, 70 eV): m/z (%):253 [M+
ꢁ29] (6), 200 (17), 199 (100), 143 (12), 115 (95), 103 (28), 87 (44), 67
(28); HRMS (EI, 70 eV): m/z: calcd for C15H29OSi: 253.1987 [M+
ꢁC2H5]; found: 253.1989.
820 cmꢁ1 (w). (Z)-9ad: GC :tR
=
7.47 min (S1); 1H NMR (400 MHz,
CDCl3, in part): d = 0.81 (d, J = 6.9 Hz, 3H), 4.04 (qd, J = 6.1, 3.5 Hz,
1H), 5.05 (brd, J = 10.0 Hz, 1H), 5.17 (dd, J = 17.0, 1.7 Hz, 1H), 5.44
(t, J = 11.0 Hz, 1H), 6.19 (t, J = 11.0 Hz, 1H), 6.35 ppm (dt, J = 17.0,
10.5 Hz, 1H).
(5S,6R,7Z,9E,11R,12S)-5,12-Di(but-3-enyl)-3,3,14,14-tetraethyl-6,11-
diiso-propyl-8-methyl-4,13-dioxa-disilahexadeca-7,9-diene
GC: tR = 20.51 min; H NMR (400 MHz, CDCl3): d
[(Z,E)-17b]:
0.50–0.58 (m,
=
(7Z,9E,5S,6R,11S,12S)-3,3,14,14-Tetraethyl-6,11-diisopropyl-5,12-dimeth-
12H), 0.90 (t, J = 7.7 Hz, 18H), 0.96 (d, J = 6.9 Hz, 3H), 1.01 (d, J =
6.6 Hz, 3H), 1.35–1.44 (m, 4H), 1.66 (d, J = 1.1 Hz, 3H), 1.88–2.02 (m,
2H), 2.02–2.12 (m, 2H), 2.34–2.38 (m, 1H), 2.64–2.71 (m, 1H), 3.47–3.57
(m, 2H), 4.84–4.97 (m, 4H), 5.07 (d, J = 9.7 Hz, 1H), 5.50 (m, 1H),
5.68–5.79 (m, 2H), 6.32 ppm (d, J = 15.65 Hz, 1H); GC-MS (EI, 70 eV):
m/z (%): 520 [M+], 333 (1), 199 (100), 115 (36), 87 (25), 67 (11).
yl-8-vinyl-4,13-dioxa-3,14-disilahexadeca-7,9-diene
[(Z,E)-17ab]:
1H NMR (300 MHz, CDCl3): d = 0.57 (m, 12H), 0.82 (d, J = 6.9 Hz,
3H), 0.84 (d, J = 6.9 Hz, 3H), 0.94 (m, 24H), 1.06 (d, J = 6.1 Hz, 3H),
1.11 (d, J = 6.1 Hz, 3H), 1.57 (ddd, J = 9.7, 7.8, 3.1 Hz, 1H), 1.78 (m,
2H), 2.15 (ddd, J = 10.7, 8.0, 3.6 Hz, 1H), 4.04 (qd, J = 6.1, 3.1 Hz,
1H), 4.04 (qd, J = 6.1, 3.6 Hz, 1H), 4.98 (dd, J = 10.7, 1.7 Hz, 1H), 5.27
(dd, J = 17.2, 1.7 Hz, 1H), 5.52 (brd, J = 10.7 Hz, 1H), 5.62 (dd, J =
16.2, 9.9 Hz, 1H), 5.97 (brd, J = 16.2 Hz, 1H), 6.46 ppm (dd, J = 17.2,
10.7 Hz, 1H); 13CNMR (75 MHz, CDCl 3): d = 5.27 (u), 5.28 (u), 7.0 (d),
20.5 (d), 20.9 (d), 21.4 (d), 21.6 (d), 22.8 (d), 23.0 (d), 28.5, 29.0 (d), 51.9
(d), 58.9 (d), 68.8 (d), 68.9 (d), 112.9 (u), 128.0 (d), 131.5 (d), 133.0 (d),
139.7 (d), 144.3 ppm (u).
Reaction of( Z)-2c with LiCuMe2:
A suspension of CuI (249 mg,
1.3 mmol) in Et2O (10 mL) at ꢁ408Cwas treated with MeLi (1.05 mL,
2.4 mmol). After the yellow mixture was stirred for 1 h, the lithioalkenyl
sulfoximine (Z)-2c, which was prepared from (Z)-1c (200 mg,
0.43 mmol) and MeLi (0.22 mL of 5% solution in Et2O, 0.43 mmol), in
Et2O (2 mL) was transferred through a cannula to the mixture. The mix-
ture was stirred for 1 h at ꢁ408Cand allowed to warm room temperature
and stirred for 8 h. Then the mixture was quenched with D2O and ex-
tracted with Et2O. The combined organic phases were dried (MgSO4)
and concentrated in vacuo. A 1H NMR spectrum showed the formation
of [D]-(E)-9c and 16c in a ratio of 7:3). Purification by chromatography
(hexane/EtOAc 98:2) gave [D]-(E)-9c (71 mg, 50%) and 16c (28 mg,
19%) as colorless liquids.
Reaction of( Z)-2b with LiCuMe2
a) A suspension of CuI (140 mg, 0.73 mmol) in Et2O (5 mL) at ꢁ408C
was treated with MeLi (0.6 mL of 5% solution in Et2O, 1.34 mmol).
After the yellow mixture was stirred for 1 h, the lithioalkenyl sulfoximine
(Z)-2b, which was prepared from the alkenyl sulfoximine (Z)-1b
(100 mg, 0.25 mmol) and MeLi (0.12 mL of 5% solution in Et2O,
0.27 mmol), in Et2O (2 mL) was added. The mixture was stirred for 1 h at
ꢁ408Cand then allowed to warm room temperature and stirred for 8 h.
The mixture was quenched with aqueous NH4Cl and extracted with Et2O.
The combined organic phases were dried (MgSO4) and concentrated in
vacuo. Purification by column chromatography (hexane) gave a mixture
of alkene (E)-9b and dimethyl alkene 16b (39 mg) in a ratio of 7:3 as a
colorless liquid. GC-MS analysis showed the formation of (E)-9b and
16b together with 5% of diene (Z,E)-17b. Separation by HPLC(pen-
tane) gave (E)-9b (27 mg, 41%) and 16b (12 mg, 18%) as colorless liq-
uids.
tert-Butyl (1R,2R,E)-2-isopropyl-1-phenylpent-3-enyloxy)dimethylsilane
([D]-(E)-9c): [a]D = +60.4 (c= 0.7 in CH2Cl2); 1H NMR (400 MHz,
CDCl3): d = ꢁ0.27 (s, 3H), 0.0 (s, 3H), 0.78 (d, J = 6.9 Hz, 3H), 0.84 (s,
9H), 0.85 (d, J = 7.2 Hz, 3H), 1.43–1.52 (m, 1H), 1.64 (d, J = 1.1 Hz,
3H), 1.87 (dt, J = 11.5, 5.8 Hz, 1H), 4.63 (d, J = 6.0 Hz, 1H), 5.30 (d, J
= 9.9 Hz, 1H), 7.17–7.29 ppm (m, 5H, Ph); 13C NMR (75 MHz, CDCl3):
d = ꢁ4.8 (d), ꢁ4.2 (d), 18.1 (d), 18.3 (u), 18.8 (d), 22.0 (d), 25.9 (d), 27.8
(d), 58.7 (d), 76.4 (d), 126.6 (d), 126.9 (d), 127.4 (d), 129.0 (d), 144.7 ppm
(u); IR (KBr): n˜ = 3029 (w), 2956 (s), 2888 (s), 2859 (s), 1464 (s), 1364
(m), 1253 (s), 1200 (w), 1126 (m), 1089 (s), 1067 (s), 976 (m), 870 cmꢁ1
Chem. Eur. J. 2008, 14, 6510 – 6528
ꢁ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
6525

H.-J. Gais et al.
(s); MS (EI, 70 eV): m/z (%): 263 (3), 262 (15), 222 (19), 221 (100), 165
(5), 115 (3), 75 (10), 73 (38); HRMS (EI, 70 eV): m/z: calcd for
C16H24OSiD: 262.1737 [M+ꢁC4H9]; found: 262.1738.
was stirred for 1 h, the alkenyl sulfoximine (E)-1c (200 mg, 0.43 mmol) in
Et2O (2 mL) was added. The mixture was allowed to warm to room tem-
perature and stirred for 4 h. Then the mixture was quenched with D2O
and extracted with Et2O. The combined organic phases were dried
(MgSO4) and concentrated in vacuo. Purification by chromatography
(hexane/EtOAc 80:20) afforded the a-methylalkenyl sulfoximine (E)-22
(2 mg, 10%) and sulfoximine [D]-(E)-1c (164 mg, 80%) (90% D) as col-
orless liquids.
tert-Butyl [(1R,2R)-2-isopropyl-4-methyl-1-phenylpent-3-enyloxy]dime-
thylsilane (16c): [a]D = +27.5 (c= 0.6 in CH2Cl2); 1H NMR (300 MHz,
CDCl3): d = ꢁ0.28 (s, 3H), 0.0 (s, 3H), 0.79 (d, J = 6.9 Hz, 3H), 0.85 (s,
9H), 0.89 (d, J = 6.7 Hz, 3H), 1.25 (d, J = 1.5 Hz, 3H), 1.48–1.57 (m,
1H), 1.69 (d, J = 1.5 Hz, 3H), 2.17 (dt, J = 11.6, 5.7 Hz, 1H), 4.66 (d, J
= 5.7 Hz, 1H), 5.08 (dp, J = 10.4, 2.8 Hz, 1H), 7.17–7.27 ppm (m, 5H,
Ph); 13C NMR (75 MHz, CDCl3): d = ꢁ5.0 (d), ꢁ4.4 (d), 17.9 (d), 18.9
(d), 21.7 (d), 25.7 (d), 26.0 (d), 28.5 (d), 53.4 (d), 76.4 (d), 123.2 (d), 126.5
(d), 126.4 (d), 127.4 (d), 133.2 (d), 145.0 ppm (u); IR (neat): n˜ = 3065
(m), 2951 (w), 2879 (w), 1637 (s), 1451 (m), 1245 (s), 1149 (w), 1011 (w),
911 (m), 865 cmꢁ1 (m); MS (EI, 70 eV): m/z (%): 333 [M+] (1), 318 (1),
375 (10), 221 (38), 201 (100), 73 (1); HRMS (EI, 70 eV): m/z: calcd for
C20H33OSi: 317.2300 [M+ꢁCH3]; found: 317.2299.
tert-Butyl-{(E,1R,2R)-2-isopropyl-1-phenyl-4-[(S)-N-methyl-phenylsulfo-
nimidoyl]pent-3-enyloxy}dimethylsilane [(E)-22]: [a]D = +58.5 (c = 0.8
in CH2Cl2); 1H NMR (300 MHz, CDCl3): d = ꢁ0.31 (s, 3H), ꢁ0.04 (s,
3H), 0.85 (d, J = 6.9 Hz, 3H), 0.88 (s, 9H), 1.05 (d, J = 6.6 Hz, 3H),
1.16 (d, J = 1.4 Hz, 3H), 1.90 (sex, J = 13.2 Hz, 1H), 2.02 (sep, J =
11.0 Hz, 1H), 2.73 (s, 3H, NMe), 4.92 (d, J = 3.0 Hz, 1H), 5.95 (d, J =
15.1 Hz, 1H), 6.86 (m, 1H), 6.85–6.95 (m, 4H), 6.96–7.02 (m, 1H, Ph),
7.48–7.53 (m, 2H, Ph), 7.55–7.60 (m, 1H, Ph), 7.81–7.89 ppm (m, 2H);
13CNMR (100 MHz, CDCl 3): d = ꢁ4.8 (d), ꢁ4.1 (d), 18.3 (u), 20.3 (d),
21.5 (d), 26.0 (d), 28.5 (d), 29.0 (d), 50.9 (d), 75.1 (d), 126.6 (d), 127.0 (d),
127.8 (d), 128.5 (d), 128.8 (d), 131.2 (d), 132.2 (d), 140.5 (u), 143.4 (u),
145.7 ppm (d); IR (neat): n˜ = 2956 (w), 2860 (w), 2801 (s), 1467 (s), 1366
(s), 1250 (s), 1143 (w), 1091 (w), 921 (m), 866 (w), 837 cmꢁ1(w); MS (EI,
70 eV): m/z (%): 471 (3) [M+], 456 (1), 428 (4), 414 (26), 365 (10), 250
(7), 221 (100), 115 (4), 75 (9); HRMS (EI, 70 eV): calcd for
C27H41NO2SSi: 471.2627 [M+]; found: 471.2626.
Reaction of( Z)-1c with LiCuMe2
a) A suspension of CuI (249 mg, 1.3 mmol) in Et2O (10 mL) at ꢁ408C
was treated with MeLi (1.05 mL, 2.4 mmol). After the yellow mixture
was stirred for 1 h, the alkenyl sulfoximine (Z)-1c (200 mg, 0.43 mmol) in
Et2O (2 mL) was added. The mixture was stirred for 1 h at ꢁ408Cand al-
lowed to room temperature and stirred for 8 h. Then the reaction mixture
was quenched with saturated NH4Cl and extracted with Et2O. The com-
bined organic phases were dried (MgSO4) and concentrated in vacuo. Pu-
rification by chromatography (EtOAc/hexane 2:98) afforded alkene (E)-
9c (98 mg, 71%) and dimethyl alkene 16c (13 mg, 9%) as colorless liq-
uids in a ratio of 9:1. When the reaction mixture was quenched with D2O
and extracted with Et2O, dried (MgSO4) concentrated in vacuo. Purifica-
tion by column chromatography (hexane/EtOAc 98:2) afforded a mixture
of [D]-(E)-9c (98% D) and 16c in a ratio of 9:1 in similar yields.
[D]-(E)-1c: [a]D
=
+62.4 (c = 4.5 in CH2Cl2); 1H NMR (300 MHz,
CDCl3): d = ꢁ0.30 (s, 3H), ꢁ0.0 (s, 3H), 0.85 (s, 9H), 0.94 (d, J =
6.9 Hz, 3H), 1.05 (d, J = 6.7 Hz, 3H), 1.85 (sex, J = 13.2 Hz, 1H), 2.02–
2.09 (m, 1H), 2.77 (s, 3H, NMe), 4.88 (d, J = 4.0 Hz, 1H), 6.86 (d, J =
10.4 Hz, 1H), 6.95–6.99 (m, 2H), 7.02–7.15 (m, 3H, Ph), 7.54–7.67 (m,
3H, Ph), 7.85–7.89 ppm (m, 2H); 13CNMR (100 MHz, CDCl 3): d = ꢁ4.8
(d), ꢁ4.1 (d), 18.3 (u), 20.3 (d), 21.5 (d), 26.0 (d), 28.5 (d), 29.0 (d), 50.9
(d), 75.1 (d), 126.6 (d), 127.0 (d), 127.8 (d), 128.5 (d), 128.8 (d), 131.2 (d),
132.2 (d), 140.5 (u), 143.4 (u), 145.7 ppm (d); IR (neat): n˜ = 3021 (m),
2956 (w), 2860 (s), 2802 (m), 1466 (s), 1388 (s), 1250 (w), 1153 (w), 1086
(w), 984 (m), 855 (w), 754 cmꢁ1 (w); MS (EI, 70 eV): m/z (%): 459 (2)
[M+ +1], 458 (5), 415 (11), 401 (31), 222 (19), 221 (100), 115 (5), 73 (47);
HRMS (EI, 70 eV): m/z: calcd for C26H38DNO2SSi: 458.2533 [M+];
found: 458.2534.
tert-Butyl (1R,2R,E)-2-isopropyl-1-phenylpent-3-enyloxy)dimethylsilane
1
[(E)-9c]: [a]D = +61.9 (c= 2.1 in CH2Cl2); H NMR (400 MHz, CDCl3):
d = ꢁ0.27 (s, 3H), 0.0 (s, 3H), 0.78 (d, J = 6.9 Hz, 3H), 0.84 (s, 9H),
0.85 (d, J = 7.2 Hz, 3H), 1.43–1.52 (m, 1H), 1.66 (dd, J = 6.3, 1.7 Hz,
3H), 1.87 (dt, J = 11.5, 5.8 Hz, 1H), 5.17 (dq, J = 15.1, 6.2 Hz, 1H),
5.34 (ddq, J
= 15.3, 9.7, 1.5 Hz, 1H), 7.17–7.29 ppm (m, 5H, Ph);
13CNMR (100 MHz, CDCl 3): d = ꢁ4.8 (d), ꢁ4.2 (d), 18.2 (d), 18.3 (u),
18.8 (d), 22.0 (d), 25.9 (d), 27.8 (d), 58.7 (d), 76.4 (d), 126.6 (d), 126.9 (d),
127.4 (d), 127.7 (d), 129.1 (d), 144.7 ppm (u); IR (neat): n˜ = 3026 (s),
2956 (w), 2887 (w), 2859 (w), 1463 (s), 1253 (w), 1198 (m), 1089 (w), 972
(s), 873 cmꢁ1 (w); MS (EI, 70 eV): m/z (%): 261 (22) [M+], 221 (100),
185 (1), 115 (5), 73 (33); HRMS (EI, 70 eV): m/z: calcd for C16H25OSi;
261.1674 [M+ꢁC4H9]; found: 261.1676.
b) A suspension of CuI (830 mg, 4.3 mmol) in Et2O (20 mL) at ꢁ408C
was treated with MeLi (3.7 mL, 8.4 mmol). After the yellow mixture was
stirred for 1 h, the alkenyl sulfoximine (E)-1c (200 mg, 0.43 mmol) in
Et2O (2 mL) was added. The mixture was stirred for 1 h at ꢁ408Cand al-
lowed to warm to room temperature and stirred for 20 h. Then the mix-
ture was quenched with saturated aqueous NH4Cl and extracted with
Et2O. The combined organic phases were dried (MgSO4) and concentrat-
ed in vacuo. Purification by chromatography (hexane/EtOAc 98:2) gave
(Z)-9c (100 mg, 72%) and 16c (8 mg, 6%) as colorless liquids in a ratio
of 9:1.
b) A suspension of CuI (124 mg, 0.65 mmol) in Et2O (5 mL) at ꢁ408C
was treated with MeLi (0.527 mL, 1.22 mmol). After the yellow mixture
was stirred for 1 h, a solution of the alkenyl sulfoximine (Z)-1c (100 mg,
0.21 mmol) in Et2O (5 mL) was added and the mixture was allowed to
stir for 1 h. Then the mixture was allowed to warm to room temperature
and stirred until TLCindicated a complete consumption of the starting
material. The mixture was quenched with ethyl acrylate (2 mmol). Then
the mixture was allowed to stir for 1 h, and treated with saturated aque-
ous NH4Cl and extracted with Et2O. The combined organic phases were
dried (MgSO4) and concentrated in vacuo. Purification by chromatogra-
phy (hexane/EtOAc 95:5) gave ester (Z)-20 (40 mg, 50%) as a colorless
liquid.
tert-Butyl (1R,2R,Z)-2-isopropyl-1-phenylpent-3-enyloxy)dimethylsilane
[(Z)-9c]: [a]D
= +25.6 (c =
3.3 in CH2Cl2); 1H NMR (300 MHz,
CDCl3): d = ꢁ0.29 (s, 3H), 0.0 (s, 3H), 0.80 (d, J = 6.9 Hz, 3H), 0.85 (s,
9H), 0.93 (d, J = 6.7 Hz, 3H), 1.20 (dd, J = 6.7, 1.7 Hz, 3H), 1.58 (sex,
J = 13.4 Hz, 1H), 2.25 (sep, J = 10.6 Hz, 1H), 4.73 (d, J = 5.0 Hz, 1H),
5.35 (m, 1H), 5.52 (dq, J = 10.7, 6.7 Hz, 1H), 7.16–7.25 ppm (m, 5H,
Ph); 13CNMR (75 MHz, CDCl 3): d = ꢁ5.0 (d), ꢁ4.3 (d), 12.87 (d), 18.1
(u), 19.2 (d), 21.7 (d), 25.8 (d), 28.4 (d), 52.3 (d), 76.0 (d), 125.9 (d), 126.5
(d), 126.7 (d), 127.4 (d), 128.9 (d), 144.1 ppm (u); IR (neat): n˜ = 3063 (s),
3016 (w), 2956 (w), 2859 (w), 1467 (s), 1253 (w), 1125 (s), 1089 (w), 977
(s), 836 cmꢁ1 (w); MS (EI, 70 eV): m/z (%): 262 (4) [M+], 261 (21), 222
(19), 221 (100), 115 (4), 73 (37); HRMS (EI, 70 eV): m/z: calcd for
C16H25OSi: 261.1674 [M+ꢁC4H9]; found: 261.1674.
A
6-(R)-(tert-butyldimethylsilyloxy)(phenyl)methyl)-4,7-di-
A
1
methyl-oct-4-enoate [(Z)-20]: H NMR (300 MHz, CDCl3): d = ꢁ0.25 (s,
3H), 0.01 (s, 3H), 0.79 (d, J = 6.7 Hz, 3H), 0.88 (s, 9H), 0.96 (d, J =
6.6 Hz, 3H), 1.27 (t, J = 7.2 Hz, 3H), 1.35–1.45 (m, 2H), 1.69 (s, 3H),
2.12 (t, J = 7.7 Hz, 1H), 4.10 (q, J = 7.9 Hz, 2H), 4.80 (d, J = 4.5 Hz,
1H), 5.25 (d, J = 10.6 Hz, 1H), 7.17–7.29 ppm (m, 5H, Ph); IR (neat):
n˜ = 3060 (m), 2957 (w), 2860 (w), 1734 (w), 1601 (s), 1463 (w), 1254 (w),
1183 (w), 1090 (w), 916 (m), 837 (w), 735 cmꢁ1 (m); GC-MS (EI, 70 eV):
m/z (%): 361 [M+ꢁ57] (5), 221 (100), 165 (2), 115 (3), 73 (26).
Reaction of( E)-2b with LiCuMe2:
A suspension of CuI (463 mg,
2.4 mmol) in Et2O (10 mL) at ꢁ408Cwas treated with MeLi (2.09 mL of
5% solution in Et2O, 4.7 mmol). After the yellow mixture was stirred for
1 h, the a-lithioalkenyl sulfoximine (E)-2b (prepared from 100 mg,
0.24 mmol, of sulfoximine (E)-1b and MeLi, 0.12 mL, 0.24 mmol) in
Et2O (2 mL) was added. The mixture was stirred for 1 h at ꢁ408Cand al-
lowed to warm to room temperature and stirred for 12 h. Then the mix-
Reaction of( E)-1c with LiCuMe2
a) A suspension of CuI (249 mg, 1.3 mmol) in Et2O (10 mL) at ꢁ408C
was treated with MeLi (1.05 mL, 2.5 mmol). After the yellow mixture
6526
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Chem. Eur. J. 2008, 14, 6510 – 6528

Sulfoximines Reactions
FULL PAPER
ture was quenched with aqueous NH4Cl and extracted with Et2O. The
combined organic phases were dried (MgSO4) and concentrated in vacuo.
Purification by chromatography (hexane) gave a mixture (40 mg) of (Z)-
9b and 16b in a ratio of 7:3 as a colorless liquid. HPLC(pentane) gave
(E)-9b (27 mg, 41%) and 16b (12 mg, 18%) as colorless liquids.
[4] I. Erdelmeier, H.-J. Gais, J. Am. Chem. Soc. 1989, 111, 1125–1126.
[5] I. Erdelmeir, Ph.D. Thesis, TU Darmstadt, 1990.
[6] a) P. Kocienski, in Organic Synthesis via Organometallics (OSM 4,
Aachen) (Eds.: D. Enders, H.-J. Gais, W. Keim), Vieweg, Wiesba-
den, 1993, pp. 203–223; b) P. Kocienski, C. Barber, Pure Appl.
Chem. 1990, 62, 1933–1940.
[7] 1,2-MR of a-halogen-substituted alkenyl borates: a) J. Gerard, L.
Hevesi, Tetrahedron 2001, 57, 9109–9121; b) Z. Huang, E. Negishi,
J. Am. Chem. Soc. 2007, 129, 14788–14792.
Triethyl [(5S,6R,Z)-6-methylnona-1,7-dien-5-yloxy]silane [(Z)-9b]: [a]D
= ꢁ27.0 (c = 0.5 in CH2Cl2); 1H NMR (300 MHz, CDCl3): d = 0.60–
0.67 (m, 6H), 0.97 (d, J = 6.9 Hz, 3H), 0.99 (t, J = 7.7 Hz, 9H), 1.45–
1.54 (m, 2H), 1.64 (dd, J = 6. 7, 1.5 Hz, 3H), 1.96–2.08 (m, 1H), 2.08–
2.22 (m, 1H), 2.57–2.69 (m, 1H), 3.59 (m, 1H), 4.92–5.06 (m, 2H), 5.28–
5.38 (m, 1H), 5.42–5.54 (m, 1H), 5.76–5.90 ppm (m, 1H); 13CNMR
(75 MHz, CDCl3): d = 5.2, (u), 7.0 (d), 13.1 (d), 16.0 (d), 30.2 (u), 33.1
(u), 36.6 (d), 75.3 (d), 114.2 (u), 123.7 (d), 132.9 (d), 138.9 ppm (d); IR
(neat): n˜ = 3078 (w), 3013 (m), 2955 (s), 2878 (s), 1641 (m), 1456 (m),
1238 (m), 1067 (s), 1009 (s), 909 (m), 850 cmꢁ1 (m); MS (CI, isobutane):
m/z (%):269 [M+] (15), 253 (3), 239 (14), 199 (43), 179 (3), 165 (6), 151
(23), 137 (100); HRMS (EI, 70 eV): m/z: calcd for C14H27OSi: 239.1831
[M+ꢁC2H5]; found: 239.1832.
[8] 1,2-MR of a-halogen-substituted alkenyl aluminates: A. Debuigne,
J. Gerard, l. Hevesi, Tetrahedron Lett. 1999, 40, 5943–5944.
[9] 1,2-MR of a-halogen-substituted alkenyl zirconates: a) E. Negishi,
K. Akiyoshi, B. OꢀConnor, K. Takagi, G. Wu, J. Am. Chem. Soc.
1989, 111, 3089–3091; b) K. Takagi, C. J. Rousset, E. Negishi, J. Am.
Chem. Soc. 1991, 113, 1440–1442; c) K. Kasai, Y. Li, R. Hara, T. Ta-
kahashi, Chem. Commun. 1998, 1989–1990; d) A. Kasatkin, R. J.
Whitby, J. Am. Chem. Soc. 1999, 121, 7039–7049.
[10] 1,2-MR of a-halogen-substituted alkenyl zincates: a) T. Harada, T.
Katsuhira, A. Oku, J. Org. Chem. 1992, 57, 5805–5807; b) T.
Harada, T. Katsuhira, D. Hara, Y. Kotani, K. Maejima, R. Kaji, A.
Oku, J. Org. Chem. 1993, 58, 4897–4907.
[11] 1,2-MR of a-alkoxy-substituted alkenyl cuprates: a) T. Fujisawa, Y.
Kurita, M. Kawashima, T. Sato, Chem. Lett. 1982, 1641–1642; b) P.
Kocienski, S. Wadman, J. Am. Chem. Soc. 1989, 111, 2363–2365;
c) C. Barber, P. Burry, P. Kocienski, M. OꢀShea, J. Chem. Soc. Chem.
Commun. 1991, 1595–1597; d) P. Le MØnez, N. Firmo, V. Fargeas, J.
Ardisson, A. Pancrazi, Synlett 1994, 995–997; e) K. Jarowicki, P. Ko-
cienski, S. Norris, M. OꢀShea, M. Stocks, Synthesis 1995, 195–198;
f) G. Hareau-Vittini, P. Kocienski, G. Reid, Synthesis 1995, 1007–
1013; g) G. Hareau-Vittini, P. Kocienski, Synlett 1995, 893–894; h) P.
Le MØnez, I. Berque, V. Fargeas, A. Pancrazi, M. E. T. H. Dau, J.
Ardisson, Synlett 1996, 1125–1128; i) A. Pommier, P. Kocienski,
Chem. Commun. 1997, 1139–1140; j) J. E. Milne, K. Jarowicki, P.
Kocienski, J. Alonso, Chem. Commun. 2002, 426–427; k) P. Le MØ-
nez, J.-D. Brion, J.-F. Betzer, A. Pancrazi, J. Ardisson, Synlett 2003,
955–958; l) A. Pommier. V. Stepanenko, K. Jarowicki, P. Kocienski,
J. Alonso, J. Org. Chem. 2003, 68, 4008–4013; m) Organic Syntheses,
Coll. Vol. 10, p. 662, 2004, Vol. 79, p. 11, 2002.
ACHTREUNG
=
=
=
CDCl3): d = 0.52–0.57 (m, 6H), 0.85 (d, J = 6.9 Hz, 3H), 0.89 (m, 9H),
1.35–1.42 (m, 2H), 1.54 (d, J = 1.5 Hz, 3H), 1.62 (d, J = 1.2 Hz, 3H),
1.86–1.99 (m, 1H), 1.99–2.14 (m, 1H), 2.34–2.46 (m, 1H), 3.46 (dq, J =
9.9, 3.71, 1H), 4.84–4.94 (m, 2H), 4.96 (m, 1H), 5.68–5.82 ppm (m, 1H);
IR (neat): n˜ = 2927 (w), 2875 (s), 1637 (s), 1458 (m), 1216 (s), 1156 (m),
1011 (m), 912 (m), 759 cmꢁ1 (w); GC-MS (EI, 70 eV): m/z (%): 253 [M+
ꢁ29] (6), 200 (17), 199 (100), 143 (12), 115 (95), 103 (28), 87 (44), 67
(28); HRMS (EI, 70 eV): m/z: calcd for C16H32OSi: 239.183119 [M+
ꢁC2H5]; found: 239.183266.
Reaction of( E)-2c with LiCuMe2:
A suspension of CuI (826 mg,
4.3 mmol) in Et2O (20 mL) at ꢁ408Cwas treated with MeLi (3.7 mL,
8.4 mmol). After the yellow mixture was stirred for 1 h, the a-lithioalken-
yl sulfoximine (E)-2c (prepared from 215 mg, 0.47 mmol, of (E)-1c and
MeLi, 0.22 mL, 0.47 mmol) in Et2O (2 mL) was transferred through a
canula. The mixture was stirred for 1 h at ꢁ408Cand allowed to warm to
room temperature and stirred for 20 h. Then the mixture was quenched
with D2O and extracted with Et2O. The combined organic phases were
1
dried (MgSO4) and concentrated in vacuo. H NMR spectroscopy showed
the formation of [D]-(Z)-9c and 16c in a ratio of 7:3. Purification by
chromatography (hexane/EtOAc 98:2) gave [D]-(Z)-9c (72 mg, 52%)
and 16c (33 mg, 23%).
[12] 1,2-MR of a-carbamoyloxy-substituted alkenyl cuprates: a) P. Le
MØnez, V. Fargeas, J. Poisson, J. Ardisson, Tetrahedron Lett. 1994,
35, 7767–7770; b) P. Ashworth, B. Broadbelt, P. Jankowski, P. Ko-
cienski, A. Pimm, R. Bell, Synthesis 1995, 199–206; c) V. Fargeas, P.
Le MØnez, I. Berque, J. Ardisson, A. Pancrazi, Tetrahedron 1996, 52,
6613–6634; d) N. D. Smith, P. J. Kocienski, S. D. A. Street, Synthesis
1996, 652–666; e) I. Berque, P. Le MØnez, P. Razon, C. Anies, A.
Pancrazi, J. Ardisson, A. Neuman, T. PrangØ, J.-D. Brion, Synlett
1998, 1132–1134.
[13] 1,2-MR of a-amino-substituted alkenyl cuprates: C. E. Neipp, J. M.
Humphrey, S. F. Martin, J. Org. Chem. 2001, 66, 531–537.
[14] 1,2-MR of a-phenylsulfenyl-substituted alkenyl cuprates: I. Creton,
I. Marek, D. Brasseur, J.-L. Jeatin, J.-F. Normant, Tetrahedron Lett.
1994, 35, 6873–6876.
[15] a) W. R. Roush, in Comprehensive Organic Synthesis, Vol. 2 (Eds.:
B. M. Trost, I. Fleming, C. H. Heathcock), Pergamon Press, Oxford,
UK, 1991, pp. 1–49; b) Y. Yamamoto, N. Asao, Chem. Rev. 1993, 93,
2207–2293; c) J. A. Marshall, J. A. Chem. Rev. 1996, 96, 31–47;
d) S. E. Denmark, J.-P. Fu, Chem. Rev. 2003, 103, 2763–2793; (d) D.
Hoppe, T. Hense, Angew. Chem. 1997, 109, 2376–2410; Angew.
Chem. Int. Ed. Engl. 1997, 36, 2282–2316.
tert-Butyl (1R,2R,Z)-2-isopropyl-1-phenylpent-3-enyloxy)dimethylsilane
([D]-(Z)-9c): [a]D = +24.6 (c = 0.7 in CH2Cl2); 1H NMR (400 MHz,
CDCl3): d = ꢁ0.26 (s, 3H), 0.02 (s, 3H), 0.82 (d, J = 6.9 Hz, 3H), 0.87
(s, 9H), 0.94 (d, J = 6.9 Hz, 3H), 1.21 (d, J = 1.7 Hz, 3H), 1.61 (sex, J
= 13.5 Hz, 1H), 2.24–2.31 (m, 1H), 4.76 (d, J = 5.0 Hz, 1H), 5.37 (m,
1H), 7.24–7.27 ppm (m, 5H, Ph); 13CNMR (100 MHz, CDCl 3): d = ꢁ5.0
(d), ꢁ4.3 (d), 12.8 (d), 18.1 (u), 19.4 (d), 21.8 (d), 25.9 (d), 28.5 (d), 52.3
(d), 76.0 (d), 126.5 (d), 126.6 (d), 127.4 (d), 128.8 (d), 144.1 ppm (u); IR
(neat): n˜ = 3063 (m), 2956 (w), 2888 (w), 1464 (w), 1253 (w), 1126 (s),
1089 (w), 976 (s), 835 cmꢁ1 (w); MS (EI, 70 eV): m/z (%): 263 (3), 262
(15), 222 (19), 221 (100), 165 (6), 115 (4), 73 (43); HRMS (EI, 70 eV):
m/z: calcd for C20H33DOSi: 262.1737 [M+ꢁC4H9]; found: 262.1740.
Acknowledgement
[16] Ni-catalyzed CC of carbamoyloxy-substituted homoallyl alcohols:
a) F.-H. PorØe, A. Clavel, J.-F. Betzer, A. Pancrazi, J. Ardisson, Tet-
rahedron Lett. 2003, 44, 7553–7556; b) F.-H. PorØe, J. Barbion, S.
Dhulut, J.-F. Betzer, A. Pancrazi, J. Ardisson, Synthesis 2004, 18,
3017–3022; c) E. de Lemos, F.-H. PorØe, A. CommerÅon, J.-F.
Betzer, A. Pancrazi, J. Ardisson, Angew. Chem. 2007, 119, 1949–
1953; Angew. Chem. Int. Ed. 2007, 46, 1919–1921.
Financial support of this work by the Deutsche Forschungsgemeinschaft
(SFB 380 and GK 440) is gratefully acknowledged. We thank Dr. Jan
Runsink for NMR spectroscopic investigations.
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Received: March 12, 2008
Published online: June 9, 2008
6528
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Chem. Eur. J. 2008, 14, 6510 – 6528