Reinvestigation of base-induced skeletal conversion via a spirocyclic intermediate of dibenzodithiocinium derivatives and a computational study using the HF/6-31G* …

K Okada, M Tanaka

Index: Okada, Keiji; Tanaka, Masato Journal of the Chemical Society. Perkin Transactions 1, 2002 , # 23 p. 2704 - 2711

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Citation Number: 12

Abstract

Treatment of 6-methyl-12-oxo-5H, 7H-dibenzo [b, g][1, 5] dithiocinium salt (1a) with methanolic KOH afforded a mixture of dibenzothiepin derivative 5 in 66% yield. The rearrangement was explained in terms of usual [2, 3]-sigmatropic shift via a spirocyclic intermediate. However, an unique rearrangement via an alternative spirocyclic intermediate was observed in 6-methyl-5H, 7H-dibenzo [b, g][1, 5] dithiocinium salt (2) to give an ...