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. 2013 Jun 12;135(23):8460-3.
doi: 10.1021/ja402891m. Epub 2013 May 30.

Oxidative Heck vinylation for the synthesis of complex dienes and polyenes

Jared H Delcamp  1 , Paul E Gormisky, M Christina White
Affiliations

Oxidative Heck vinylation for the synthesis of complex dienes and polyenes

Jared H Delcamp et al. J Am Chem Soc. .

Abstract

We introduce an oxidative Heck reaction for selective complex diene and polyene formation. The reaction proceeds via oxidative Pd(II)/sulfoxide catalysis that retards palladium-hydride isomerizations which previously limited the Heck manifold's capacity for furnishing stereodefined conjugated dienes. Limiting quantities of nonactivated terminal olefins (1 equiv) and slight excesses of vinyl boronic esters (1.5 equiv) that feature diverse functionality can be used to furnish complex dienes and polyenes in good yields and excellent selectivities (generally E:Z = >20:1; internal:terminal = >20:1). Because this reaction only requires prior activation of a single vinylic carbon, improvements in efficiency are observed for synthetic sequences relative to ones featuring reactions that require activation of both coupling partners.

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Figures

Scheme 1
Scheme 1. Streamlined Synthesis of the Macrolactin A C12-C24 Segment
Scheme 2
Scheme 2. Streamlined Synthesis of the Amphidinolide C C17-C29 Segment
Scheme 3
Scheme 3. Synthesis of a Highly Conjugated Retinoid
See this image and copyright information in PMC

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