Synthetic scope, computational chemistry and mechanism of a base induced 5-endo cyclization of benzyl alkynyl sulfides

…, Á Castillo, A Greer, LK Montemayer, EE Sheepwash…

Index: Motto, John M.; Castillo, Alvaro; Greer, Alexander; Montemayer, Laura K.; Sheepwash, Erin E.; Schwan, Adrian L. Tetrahedron, 2011 , vol. 67, # 5 p. 1002 - 1010

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Citation Number: 19

Abstract

We present an experimental and computational study of the reaction of aryl substituted benzyl 1-alkynyl sulfides with potassium alkoxide in acetonitrile, which produces 2-aryl 2, 3- dihydrothiophenes in poor to good yields. The cyclization is most efficient with electron withdrawing groups on the aromatic ring. Evidence indicates there is rapid exchange of protons and tautomerism of the alkynyl unit prior to cyclization. Theoretical calculations ...