Synfacts 2011(1): 0095-0095  
DOI: 10.1055/s-0030-1259193
Organo- and Biocatalysis
© Georg Thieme Verlag Stuttgart ˙ New York

An Umpolung Reaction of Aldehydes with Arynes

Contributor(s): Benjamin List, Olga Lifchits
A. T. Biju, F. Glorius*
Westfälische Wilhelms-Universität Münster, Germany
Further Information

Publication History

Publication Date:
21 December 2010 (online)


Biju and Glorius report an unprecedented N-heterocyclic carbene (NHC) catalyzed hydroacylation of arynes. In this umpolung reaction, various aldehydes 1 are activated via the Breslow intermediate A to react with arynes generated in situ from precursors 2. The authors propose a mechanism involving either a concerted (B) or a stepwise (C D) addition-protonation sequence. An analogy to the more explored [2+3] cycloadditions of arynes and 1,3-dipoles is invoked for the concerted mechanism. Competition experiments provided insight into the rates of individual steps.