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Synthesis 2010(19): 3259-3262  
DOI: 10.1055/s-0030-1258196
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart ˙ New York

Diene-Ligated Iridium Complexes as Catalysts for Allylation and Methallylation Reactions of Ketones

Timothy J. Barker, Elizabeth R. Jarvo*
Department of Chemistry, University of California, Irvine 92697-2025, USA
Fax: +1(949)8249920; e-Mail: erjarvo@uci.edu;
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Publication History

Received 30 June 2010
Publication Date:
04 August 2010 (online)

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Abstract

An iridium-catalyzed allylation reactions of ketones using dienes as ligands has been developed. A variety of ketones underwent allylation and methallylation reactions at room temperature in good yields under these conditions. Competition experiments demonstrate that the reaction is selective for electron-deficient ketones.

Key words

iridium - allylation - diene ligands - boric acid

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6

No enantiomeric excess was observed in the products of the reactions with the chiral ligands in Table  [¹] .

9

An alternative role for boric acid would be to transmetalate with an iridium chloride precatalyst to form a more active iridium hydroxide complex. Iridium alkoxide complexes, e.g., [Ir(cod)OMe]2, are competent catalysts for the reaction, consistent with this hypothesis.