Hydrostannylation–Cross-Coupling Strategy for the Stereoselective Synthesis of Alkylidenemalonates and Related α,β-Unsaturated Esters

Author： Fujiwara Shinichi Cadou Romain Yamaoka Yousuke Takasu Kiyosei Yamada Ken-ichi

Publisher： Blackwell Publishing

E-ISSN： 1099-0690|2015|6|1264-1272

ISSN： 1434-193X

Source： European Journal of Organic Chemistry, Vol.2015, Iss.6, 2015-02, pp. : 1264-1272

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Abstract

A method for the stereoselective synthesis of alkylidenemalonates and related α,β-unsaturated esters by a hydrostannylation–cross-coupling process has been developed. Pd-catalyzed and radical hydrostannylation of propiolate derivatives stereoselectively provided α-alkoxycarbonyl (E)- and (Z)-vinylstannanes, respectively, which were then converted into alkylidenemalonates by the Stille coupling reaction. A one-pot process was also realizable for the Pd-catalyzed reactions. Pd-catalyzed and radical hydrostannylation of propiolate derivatives stereoselectively provided α-alkoxycarbonyl (E)- and (Z)-vinylstannanes, respectively, which were then converted into alkylidenemalonates by the Stille coupling reaction. A one-pot process was also realizable for the Pd-catalyzed reactions.