Two-step synthesis of chiral fused tricyclic scaffolds from phenols via desymmetrization on nickel

Ravindra Kumar, Yoichi Hoshimoto, Eri Tamai, Masato Ohashi and Sensuke Ogoshi ()
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Ravindra Kumar: Osaka University
Yoichi Hoshimoto: Osaka University
Eri Tamai: Osaka University
Masato Ohashi: Osaka University
Sensuke Ogoshi: Osaka University

Nature Communications, 2017, vol. 8, issue 1, 1-7

Abstract: Abstract Tricyclic furan derivatives with multiple chiral centers are ubiquitous in natural products. Construction of such tricyclic scaffolds in a stereocontrolled, step-economic, and atom-economic manner is a key challenge. Here we show a nickel-catalyzed highly enantioselective synthesis of hydronaphtho[1,8-bc]furans with five contiguous chiral centers via desymmetrization of alkynyl-cyclohexadienone by oxidative cyclization and following formal [4 + 2] cycloaddition processes. Alkynyl-cyclohexadienone was synthesized in one step from easily accessible phenols. This reaction represents excellent chemo-selectivity, regio-selectivity, diastereo-selectivity, and enantio-selectivity (single diastereomer, up to 99% ee). An extraordinary regioselectivity in the formal [4 + 2] cycloaddition step with enones revealed the diverse reactivity of the nickelacycle intermediate. Desymmetrization of alkynyl-cyclohexadienones via oxidative cyclization on nickel was supported by the isolation of a nickelacycle from a stoichiometric reaction. Enantioenriched tricyclic products contain various functional groups such as C=O and C=C. The synthetic utility of these products was demonstrated by derivatization of these functional groups.

Date: 2017
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DOI: 10.1038/s41467-017-00068-8

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