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. 2010 Apr 14;132(14):5027-9.
doi: 10.1021/ja100185p.

Enantioselective polyene cyclization via organo-SOMO catalysis

Sebastian Rendler  1 , David W C Macmillan
Affiliations

Enantioselective polyene cyclization via organo-SOMO catalysis

Sebastian Rendler et al. J Am Chem Soc. .

Abstract

The first organocatalytic enantioselective radical polycyclization has been accomplished using singly occupied molecular orbital (SOMO) catalysis. The presented strategy relies on a selective single-electron oxidation of chiral enamines formed by condensation of polyenals with an imidazolidinone catalyst employing a suitable copper(II) oxidant. The reaction proceeds under mildly acidic conditions at room temperature and shows compatibility with an array of electron-poor as well as electron-rich functional groups. Upon termination by radical arylation followed by subsequent oxidation and rearomatization, a range of polycyclic aldehydes were accessed (12 examples, 54-77% yield, 85-93% ee). The enantioselective formation of up to six new carbocycles in a single catalyst-controlled cascade is described. Evidence for a radical-based cascade mechanism is indicated by a series of experimental results.

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Figures

Scheme 1
Scheme 1
Enantioselective Polycyclization via SOMO Catalysis.
Scheme 2
Scheme 2
Extended Ring Systems by Organo-SOMO Catalysis.a
See this image and copyright information in PMC

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