Addition of NOCl to cyclic vinylsilanes: An unexpected reversal of regiochemistry

Article abstract of DOI:10.1016/S0040-4039(01)00190-3

NOCl adds to cyclic vinylsilanes in a syn manner with NO⁺ bonding to the β-carbon and Cl^- to the α-carbon, which is a reversal of the regiochemistry expected from the β-silicon effect. The adducts dimerize to a single diastereomer containing enantiomeric pairs and/or give secondary products on further reaction.