Diels-Alder Reactions of S-Vinyl-S-Arylsulfoximines

Richard S. Glass, Karl Reineke, Michael Shanklin

Research output: Contribution to journalArticle

32 Scopus citations

Abstract

Cyclopentadiene and the known S-p-tolyl-S-vinyl-A-phthalimidosulfoximine (1a) undergo Diels-Alder reaction to give a mixture of cycloadducts in excellent yield. The structures of the cycloadducts including stereochemistry are assigned by 1 H NMR spectroscopy. The crystal and molecular structure of the major cycloadduct 5d, n = 1, G = 1,2-C6 H4(CO)2 N was determined unequivocally by X-ray crystallographic techniques. Treatment of this major cycloadduct with hydrazine in ethanol resulted in conversion of the sulfoximine to sulfoxide group concomitant with reduction of the carbon-carbon double bond. Use of allyl alcohol as solvent in this reaction allowed conversion to the corresponding unsaturated sulfoxide 8. The previously unknown S-p-tolyl-S-vinyl-N-(p-tolylsulfonyl)-sulfoximine (1b) is somewhat more reactive than phenyl vinyl sulfone and undergoes Diels-Alder reactions with cyclic and acyclic 1,3-dienes in 81-95% yield. The endo selectivity of vinylsulfoximine 1b is 9:2 with cyclopentadiene and 93:7 with 1,3-cyclohexadiene. With 2-methyl-1,3-butadiene the para adduct is produced regioselectively in a ratio of 4:1. Although formation of the endo adducts from vinylsulfoximine 1b and “cyclopentadiene and 1,3-cyclohexadiene is not diastereoselective, the diastereomers can be separated by HPLC. The cycloadducts from 1,3-cyclohexadiene and vinylsulfoximine 1b have been converted to bicyclo[2.2.2]oct-2-ene and bicyclo-[2.2.2]oct-2-en-5-one.

Original languageEnglish (US)
Pages (from-to)1527-1533
Number of pages7
JournalJournal of Organic Chemistry
Volume49
Issue number9
DOIs
StatePublished - Sep 1984

ASJC Scopus subject areas

  • Organic Chemistry

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