Captodative substituent effects XXI. : Synthesis of selenenylated captodative olefins via selenenyl halide addition to olefins bearing electron-withdrawing substituents

doi:10.1016/S0040-4020(01)96649-9

Tetrahedron

Volume 41, Issue 12, 1985, Pages 2527-2543

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Abstract

Addition of methane- and benzeneselenenyl bromide or chloride and benzene sulfenyl chloride to carbon-carbon double bonds substituted by electronwithdrawing groups is achieved in solvents of different polarity. Two regioisomeric adducts $6$ and $7$ or $8$ and $9$ are generally formed, which can be interconverted by equilibration in refluxing acetonitrile. It is of mechanistic interest that the regioisomers may also derive from selenenyltrihalide adducts. In comparison to acrylic esters, the propiolic ester reacts more slowly, producing mainly the α-selenenyl adduct. Dehydrohalogenation of adducts provides a general and valuable method for the preparation of olefins carrying methyl or phenylselenenyl groups in α-position to electron-withdrawing substituents.

References (33)

Z. Janousek et al.
J. Organometal. Chem.
(1983)
J.-N. Denis et al.
Tetrahedron Letters
(1982)
R. Verbruggen et al.
Chimia
(1975)
Captodative Substitution Effect Part XX : S. Mignani, Z. Janousek, R. Merényi et H.G. Viehe, Bull. Soc. Chim. France,...
W.H. MuellerL. Rasteikiene et al.
Russ. Chem. Rev.
(1977)
G.A. Jones et al.
J. Chem. Soc., Perkin Trans II
(1983)
W.A. Smit et al.
Acc. Chem. Res.
(1979)
G.H. Schmid et al.
K.C. Nicoleaou
Tetrahedron Report, Tetrahedron
(1981)
M. Ihara et al.
J. Am. Chem. Soc.
(1983)
V.M. Csizmadia et al.
J. Chem. Soc., Perkin Trans. II
(1977)

W.A. Thaler et al.

J. Am. Chem. Soc.

(1968)

K.D. Gundermann

Intra-Science Chem. Rept

(1972)

S.A. Heininger et al.

C.A.

(1959)

H. Chartier

Bull. Soc. Chim. France

(1972)

M.G. Linkova et al.

Izv. Akad. Nauk SSSR, Ser. Khim.

(1971)

F.R. Tantasheva et al.

Zh. Org. Khim.

(1978)

D.I. Relyea et al.

C.A.

(1981)

G.H. Schmid et al.

Tetrahedron Letters

(1983)

A.E. Feiring

J. Org. Chem.

(1980)

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¹: Captodative Substitution Effect Part XX : S. Mignani, Z. Janousek, R. Merényi et H.G. Viehe, Bull. Soc. Chim. France, submitted.

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Captodative substituent effects XXI. 1: Synthesis of selenenylated captodative olefins via selenenyl halide addition to olefins bearing electron-withdrawing substituents

Abstract

J. Organometal. Chem.

Tetrahedron Letters

Chimia

Russ. Chem. Rev.

J. Chem. Soc., Perkin Trans II

Acc. Chem. Res.

Tetrahedron Report, Tetrahedron

J. Am. Chem. Soc.

J. Chem. Soc., Perkin Trans. II

J. Am. Chem. Soc.

Intra-Science Chem. Rept

C.A.

Bull. Soc. Chim. France

Izv. Akad. Nauk SSSR, Ser. Khim.

Zh. Org. Khim.

C.A.

Tetrahedron Letters

J. Org. Chem.

Captodative substituent effects XXI. ¹: Synthesis of selenenylated captodative olefins via selenenyl halide addition to olefins bearing electron-withdrawing substituents