title: Rhodium(III)/copper(II)-promoted trans-selective heteroaryl acyloxylation of alkynes: stereodefined access to trans-enol esters.
abstract: Enol esters are versatile synthetic building blocks which can be elaborated by a wide variety of transformations. The classical synthesis by O-selective enolate acylation often hampers control of the E/Z selectivity with highly substituted substrates. A rhodium(III)/copper(II)-mediated process is reported to provide tetrasubstituted enol esters in a trans-selective fashion. Overall, the reaction consists of a heteroaryl acyloxylation of alkynes. The process is initiated by a rhodium(III)-catalyzed C2-selective activation of electron-rich heteroarenes, such as benzofuran, furan, and thiophene. Upon addition across an alkyne, a transmetalation to copper(II) enables reductive CO bond formation. The transformation allows the three-component couplings of heteroarenes, alkynes, and carboxylic acids. Application of the method in the functionalization of bioactive furocoumarin natural products is also described.
authors.affiliation: Laboratory of Asymmetric Catalysis and Synthesis, EPFL SB ISIC LCSA, BCH 4305, 1015 Lausanne (Switzerland) http://isic.epfl.ch/lcsa.
authors.forename: Manh V
authors.initials: MV
authors.lastname: Pham
authors.forename: Nicolai
authors.initials: N
authors.lastname: Cramer
keywords: CH activation; bimetallic catalysis; copper; enol esters; rhodium