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Synfacts 2014; 10(12): 1275
DOI: 10.1055/s-0034-1379596
Metal-Catalyzed Asymmetric Synthesis and Stereoselective Reactions
© Georg Thieme Verlag Stuttgart · New York

Iridium-Catalyzed Allylic Substitution of Silyl Dienolates

Contributor(s):
Hisashi Yamamoto
,
Yasushi Shimoda
Chen M, Hartwig JF * University of California, Berkeley, USA
Iridium-Catalyzed Regio- and Enantioselective Allylic Substitution of Silyl Dienolates Derived from Dioxinones.

Angew. Chem. Int. Ed. 2014;
53: 12172-12176
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Publication History

Publication Date:
18 November 2014 (online)

 
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Key words

allylic alkylation - dienolates - iridium

Significance

The allylic substitution at the γ-position of 1,3-dicarbonyl compounds has not been studied so far. Herein, the authors present the iridium phosphoramidite catalyzed allylic substitution reaction with high regio- and enantioselectivities. Silyl dienolates act as synthetic equivalents of β-keto ester dianions.


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Comment

In this reaction, the combination of a leaving group on the allylic substrates and a chiral phosphoramidite ligand plays a crucial role to obtain high regioselectivities. The dioxinone moiety in the products can be converted easily into useful structures such as teramic acids.


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