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Construction of 1,3-Dithio-Substituted Tetralins by [1,5]-Alkylthio Group Transfer Mediated Skeletal Rearrangement
Naoya Hisano1, Yuto Kamei2, Yaoki Kansaku2
1Department of Applied Chemistry, Graduate School of Engineering , Tokyo University of Agriculture and Technology , 2-24-16 Nakacho , Koganei , Tokyo 184-8588 , Japan.
Abstract:
A novel skeletal rearrangement involving a [1,5]-alkylthio group transfer/cyclization sequence is described. Treatment of benzylidene malonates having a thioketal moiety at the homobenzyl position with a catalytic amount of Sc(OTf)3 afforded alkylthio group rearranged adducts in good chemical yields. Detailed investigation of the reaction mechanism revealed that an intramolecular conjugate addition/ring opening sequence (not through-space transfer) is the key to achieving this reaction.
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