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

Add time:08/04/2019    Source:sciencedirect.com

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% EtOH with a greater neighboring group participation than in 97% TFE. It has been concluded that in solvolytic reactions of allylic substrates a pronounced neighboring group participation (k2/k1 = 900) may occur only with very strong internal nucleophiles, and in solvents which can not form strong hydrogen bonds with these nucleophiles.

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