Preparation of allenic sulfones and allenes from the selenosulfonation of acetylenes

{beta}-(phenylseleno)vinyl sulfones 2 are readily obtained from the free-radical selenosulfonation of acetylenes. Compounds 2 isomerize to allyl sulfones 4 under base-catalyzed conditions in nearly quantitative yield, with high stereoselectivity favoring the Z configuration. Allyl sulfones 4 afford...

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Bibliographic Details
Published in:Journal of organic chemistry 1989-08, Vol.54 (17), p.4146-4153
Main Authors: Back, Thomas G, Krishna, M. Vijaya, Muralidharan, K. Raman
Format: Article
Language:English
Subjects:
400201 - Chemical & Physicochemical Properties
ACETYLENE
Aliphatic compounds
ALKYNES
ALLENE
CHEMICAL REACTIONS
Chemistry
DATA
DATA ANALYSIS
DIENES
ELEMENTS
Exact sciences and technology
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
Organic chemistry
ORGANIC COMPOUNDS
POLYENES
Preparations and properties
SELENIUM
SEMIMETALS
SULFONATION
SYNTHESIS
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Summary:{beta}-(phenylseleno)vinyl sulfones 2 are readily obtained from the free-radical selenosulfonation of acetylenes. Compounds 2 isomerize to allyl sulfones 4 under base-catalyzed conditions in nearly quantitative yield, with high stereoselectivity favoring the Z configuration. Allyl sulfones 4 afford generally high yields of allenic sulfones 1 when subjected to oxidation with m-chloroperbenzoic acid or tert-butyl hydroperoxide, followed by selenoxide syn-elimination. The sulfone-stabilized anion intermediates in the isomerizations of 2 to 4 can be alkylated, deuterated, or silylated in the {alpha}-position prior to oxidation, providing allenic sulfones with an additional {alpha}-substituent. In some cases, spontaneous elimination of the phenylseleno group occurred, producing the allenic sulfone without the need for an oxidation step. Desulfonylation of allyl sulfones 4f, 4c, and 25 with sodium amalgam afforded vinyl selenides that were converted to allenes in moderate to good yields by oxidation-elimination. The copper-catalyzed coupling of allyl sulfones 4 with Grignard reagents comprises an alternative route to vinyl selenide precursors of allenes. These procedures permit the synthesis of various {alpha}- and {gamma}-substituted allenic sulfones and allenes from acetylenes.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo00278a030