Enantioselective Synthesis of (–)-Stemoamide

Xianwei Mi; Yan Wang; Lili Zhu; Renxiao Wang; Ran Hong

doi:10.1055/s-0032-1317499

Synthesis, Table of Contents

Synthesis 2012; 44(22): 3432-3440
DOI: 10.1055/s-0032-1317499

feature article

Enantioselective Synthesis of (–)-Stemoamide

Xianwei Mi

^aKey Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China Email: rhong@sioc.ac.cn

^bState Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China

,

Yan Wang

^aKey Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China Email: rhong@sioc.ac.cn

,

Lili Zhu

^aKey Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China Email: rhong@sioc.ac.cn

,

Renxiao Wang

^bState Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China

,

Ran Hong*

^aKey Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China Email: rhong@sioc.ac.cn

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Abstract

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Dedicated to Professor Guo-Qiang Lin on the occasion of his 70^th birthday

Abstract

An enantioselective synthesis of (–)-stemoamide is presented. Noyori’s ruthenium complex catalyzed asymmetric transfer hydrogenation of an alkynone delivered the (S)-C8 stereogenic center in 97.7% ee. An iron(III) chloride promoted and bioinspired N-iminium ion cyclization afforded a 3:1 ratio of two diastereomers in favor of the cis-isomer. The diastereomeric ratio was enriched to 50:1 by a silver-catalyzed cycloisomerization. The subsequent dynamic ruthenium-catalyzed CO-insertion reaction secured an enantioselective total synthesis of (–)-stemoamide in 18% overall yield with high optical purity.

Key words

carbonylation - biomimetic synthesis - asymmetric transfer hydrogenation - iminium ion cyclization - stemoamide

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References

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Supplementary Material

Supporting Information