Base catalyzed rearrangement of π-conjugated sulfur and selenium bridged propargylic systems

Samuel Braverman; Yossi Zafrani; Hugo E. Gottlieb

doi:10.1016/S0040-4020(01)00923-1

Base catalyzed rearrangement of π-conjugated sulfur and selenium bridged propargylic systems

Samuel Braverman, Yossi Zafrani, Hugo E. Gottlieb

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

23 Scopus citations

Abstract

A series of novel π-conjugated bis-propargylic sulfides, selenides, sulfoxides and sulfones have been prepared. In the presence of amine bases these compounds underwent facile isomerization to the corresponding allenes, followed by a tandem cyclization and aromatization of the latter via a diradical intermediate. While the reactions of sulfones and sulfoxides were almost spontaneous and proceeded in practically quantitative yield, the sulfides and selenides exhibited modest reactivity and required more polar solvents to afford the corresponding thiophenes and selenophenes. Some mechanistic studies and DNA cleaving properties are also presented.

Original language	English
Pages (from-to)	9177-9185
Number of pages	9
Journal	Tetrahedron
Volume	57
Issue number	44
DOIs	https://doi.org/10.1016/S0040-4020(01)00923-1
State	Published - 29 Oct 2001

Bibliographical note

Funding Information:
The financial support of this study by the Israel Science Foundation is gratefully acknowledged. We are also very much indebted to Dr Shai Rahimipour of the Weizmann Institute of Science for performing the DNA testing.

Keywords

Acetylenes
Allenes
Cyclizations
Radicals
Rearrangements
Sulfur and selenium compounds

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10.1016/S0040-4020(01)00923-1

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abstract = "A series of novel π-conjugated bis-propargylic sulfides, selenides, sulfoxides and sulfones have been prepared. In the presence of amine bases these compounds underwent facile isomerization to the corresponding allenes, followed by a tandem cyclization and aromatization of the latter via a diradical intermediate. While the reactions of sulfones and sulfoxides were almost spontaneous and proceeded in practically quantitative yield, the sulfides and selenides exhibited modest reactivity and required more polar solvents to afford the corresponding thiophenes and selenophenes. Some mechanistic studies and DNA cleaving properties are also presented.",

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note = "Funding Information: The financial support of this study by the Israel Science Foundation is gratefully acknowledged. We are also very much indebted to Dr Shai Rahimipour of the Weizmann Institute of Science for performing the DNA testing. ",

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T1 - Base catalyzed rearrangement of π-conjugated sulfur and selenium bridged propargylic systems

AU - Braverman, Samuel

AU - Zafrani, Yossi

AU - Gottlieb, Hugo E.

N1 - Funding Information: The financial support of this study by the Israel Science Foundation is gratefully acknowledged. We are also very much indebted to Dr Shai Rahimipour of the Weizmann Institute of Science for performing the DNA testing.

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Y1 - 2001/10/29

N2 - A series of novel π-conjugated bis-propargylic sulfides, selenides, sulfoxides and sulfones have been prepared. In the presence of amine bases these compounds underwent facile isomerization to the corresponding allenes, followed by a tandem cyclization and aromatization of the latter via a diradical intermediate. While the reactions of sulfones and sulfoxides were almost spontaneous and proceeded in practically quantitative yield, the sulfides and selenides exhibited modest reactivity and required more polar solvents to afford the corresponding thiophenes and selenophenes. Some mechanistic studies and DNA cleaving properties are also presented.

AB - A series of novel π-conjugated bis-propargylic sulfides, selenides, sulfoxides and sulfones have been prepared. In the presence of amine bases these compounds underwent facile isomerization to the corresponding allenes, followed by a tandem cyclization and aromatization of the latter via a diradical intermediate. While the reactions of sulfones and sulfoxides were almost spontaneous and proceeded in practically quantitative yield, the sulfides and selenides exhibited modest reactivity and required more polar solvents to afford the corresponding thiophenes and selenophenes. Some mechanistic studies and DNA cleaving properties are also presented.

KW - Acetylenes

KW - Allenes

KW - Cyclizations

KW - Radicals

KW - Rearrangements

KW - Sulfur and selenium compounds

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SN - 0040-4020

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JO - Tetrahedron

JF - Tetrahedron

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ER -

Base catalyzed rearrangement of π-conjugated sulfur and selenium bridged propargylic systems

Abstract

Bibliographical note

Keywords

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