D
Synlett
P. K. Chinthakindi et al.
Letter
O
P
NH
O
NH
n-BuLi
O
OEt
OEt
S
S
–78 °C
Ar
R
Ar
RCHO
Li
Li
O
S
O
P
O
S
n-BuLi
BuH
O
P
O
Li
O
P
EtO
EtO
NH
Ar
NH
Ar
EtO
EtO
NH2
Ar
O
P
O
S
S
EtO
EtO
NH2
-
EtO
EtO
H
H
Ar
Li
O
NH
NH
O
O
P
S
Ar
S
Ar
EtO
EtO
– P(O)(OEt) OLi
2
O
R
Li
R
O
O
S
NH
Ar
EtO
EtO
threo configuration is kinetically favored
E
O
O
S
P
NH
Ar
EtO
EtO
P
O
O
R
R
H
Li
O
O
NH
NH
O
S
R
S
Ar
Ar
EtO
EtO
P
2
– P(O)(OEt) OLi
O
R
erythro configuration is kinetically disfavored
Z
Scheme 3 Plausible reaction mechanism
In conclusion, we have developed a novel methodology
to access vinylic NH-sulfoximines, removing the use of pro-
tection and deprotection group strategies. The procedure is
compatible with a wide range of substrates and functional
groups and offers excellent yields and E-selectivity. We an-
ticipate that the current methodology will find broad utility
for the synthesis of vinylic sulfoximines as a precursor in
organic synthesis and medicinal chemistry applications.
(4) Lemasson, F. Doctoral Dissertation; RWTH Aachen University:
Germany, 2008, retrieved from http://publications.rwth-
aachen.de/record/50343/files/Lemasson_Fabien.pdf.
(
(
(
(
5) Pyne, S. G.; Dong, Z. Tetrahedron Lett. 1999, 40, 6131.
6) Harmata, M.; Ghosh, S. K. Org. Lett. 2001, 3, 3321.
7) Pyne, S. G. Tetrahedron Lett. 1986, 27, 1691.
8) (a) Glass, R. S.; Reineke, K.; Shanklin, M. J. Org. Chem. 1984, 49,
1527. (b) Craig, D.; Geach, N. J. Tetrahedron: Asymmetry 1991, 2,
1177. (c) Craig, D.; Geach, N. J.; Pearson, C. J.; Slawin, A. M. Z.;
White, A. J. P.; Williams, D. J. Tetrahedron 1995, 51, 6071.
(d) David, D. M.; Bakavoli, M.; Pyne, S. G.; Skelton, B. W.; White,
Acknowledgment
A. H. Tetrahedron 1995, 51, 12393.
(
9) (a) Tiwari, S. K.; Gais, H.-J.; Lindenmaier, A.; Babu, G. S.; Raabe,
G.; Reddy, L. R.; Köhler, F.; Günter, M.; Koep, S.; Iska, V. B. R.
J. Am. Chem. Soc. 2006, 128, 7360. (b) Koep, S.; Gais, H.-J.; Raabe,
G. J. Am. Chem. Soc. 2003, 125, 13243. (c) Günter, M.; Gais, H.-J.
J. Org. Chem. 2003, 68, 8037. (d) Schleusner, M.; Gais, H.-J.;
Koep, S.; Raabe, G. J. Am. Chem. Soc. 2002, 124, 7789.
This work is based on the research supported in part by the National
Research Foundation of South Africa for the Grant 87706. We are also
grateful to UKZN for postdoctoral fellowships to P.K.C., G.C.N. and for
additional financial support.
(
1
e) Erdelmeier, I.; Gais, H.-J.; Lindner, H. J. Angew. Chem. Int. Ed.
986, 25, 935.
Supporting Information
(
10) Kahraman, M.; Sinishtaj, S.; Dolan, P. M.; Kensler, T. W.; Peleg,
S.; Saha, U.; Chuang, S. S.; Bernstein, G.; Korczak, B.; Posner, G.
H. J. Med. Chem. 2004, 47, 6854.
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0035-1561573.
S
u
p
p
ortioIgnfrm oaitn
S
u
p
p
ortioIgnfrm oaitn
(
(
(
11) Hwang, K.-J. Bull. Korean Chem. Soc. 2000, 21, 125.
12) McGrath, M. J.; Bolm, C. Beilstein J. Org. Chem. 2007, 3, 33.
13) (a) Craig, D.; Geach, N. J. Synlett 1993, 481. (b) Bailey, P. L.;
Clegg, W.; Jackson, R. F. W.; Meth-Cohn, O. J. Chem. Soc., Perkin
Trans. 1 1993, 343. (c) Paley, R. S.; Snow, S. R. Tetrahedron Lett.
References and Notes
(1) Lücking, U. Angew. Chem. Int. Ed. 2013, 52, 9399.
(2) Sparks, T. C.; Watson, G. B.; Loso, M. R.; Geng, C.; Babcock, J. M.;
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(
14) Sklute, G.; Bolm, C.; Marek, I. Org. Lett. 2007, 9, 1259.
15) Tamura, Y.; Sumoto, K.; Minamikawa, J.; Ikeda, M. Tetrahedron
Lett. 1972, 13, 4137.
(
3) Nordqvist, A.; Nilsson, M. T.; Röttger, S.; Odell, L. R.; Krajewski,
W. W.; Evalena Andersson, C.; Larhed, M.; Mowbray, S. L.;
Karlén, A. Bioorg. Med. Chem. 2008, 16, 5501.
(
©
Georg Thieme Verlag Stuttgart · New York — Synlett 2016, 27, A–E