Angewandte Chemie. International edition in English 2014-10-13

An alternative to the classical α-arylation: the transfer of an intact 2-iodoaryl from ArI(O₂CCF₃)₂.

Zhiyu Jia, Erik Gálvez, Rosa María Sebastián, Roser Pleixats, Ángel Álvarez-Larena, Eddy Martin, Adelina Vallribera, Alexandr Shafir

Index: Angew. Chem. Int. Ed. Engl. 53(42) , 11298-301, (2014)

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Abstract

The α-arylation of carbonyl compounds is generally accomplished under basic conditions, both under metal catalysis and via aryl transfer from the diaryl λ(3)-iodanes. Here, we describe an alternative metal-free α-arylation using ArI(O2CCF3)2 as the source of a 2-iodoaryl group. The reaction is applicable to activated ketones, such as α-cyanoketones, and works with substituted aryliodanes. This formal C-H functionalization reaction is thought to proceed through a [3,3] rearrangement of an iodonium enolate. The final α-(2-iodoaryl)ketones are versatile synthetic building blocks.© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.