Tetrahedron

A search for maximal neighboring group participation in Solvolyses of allylic substrates. Ethanolysis of 2-(ω-alkylthioalkyl)-3-methyl-2-cyclohexenyl p-nitrobenzoates

BS Jursic, M Ladika, DE Sunko

Index: Jursic, Branko S.; Ladika, Mladen; Sunko, Dionis E. Tetrahedron, 1993 , vol. 49, # 13 p. 2717 - 2728

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Citation Number: 2

Abstract

The solvolysis of 2-(ω-methylthioalkyl)-and 2-(ω-benzylthioalkyl)-3-methyl-2-cyclohexenyl p- nitrobenzoates 5 and 6 in 80 vol% ethanol includes several competitive reactions. Path k1 is a stepwise process (kH/kD= 1.18–1.20) which includes allylic cation 9 as a reaction intermediate, while path k2 involves a neighboring sulfur participation (kH/kD= 1.01–1.03) and formation of an intermediate cyclic sulfonium cation 10. Esters 5 and 6 solvolyze in 80 ...