Evidence for Atropisomerism in Polycyclic γ-Butenolides: Synthesis, Scope, and Spectroscopic Studies.

Design and development of a domino cyclative approach for the synthesis of new polycyclic γ-butenolides from β-aryl-Z-enoate propargylic alcohols, through the interception of an intermediate of the Z-enoate-assisted Meyer-Schuster rearrangement, has been reported. A systematic NMR analysis of various derivatives of this class revealed and supported the potential atropisomerism associated with them. These molecules represent first examples of butenolide ring-based atropisomeric compounds in organic chemistry. The synthetic process involves a synchronous construction of both rings with concurrent creation of the potential stereogenic rotational axis.