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Synthesis 2012; 44(22): 3432-3440
DOI: 10.1055/s-0032-1317499
DOI: 10.1055/s-0032-1317499
feature article
Enantioselective Synthesis of (–)-Stemoamide
Further Information
Publication History
Received: 13 August 2012
Accepted after revision: 02 October 2012
Publication Date:
25 October 2012 (online)
Dedicated to Professor Guo-Qiang Lin on the occasion of his 70th 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 - stemoamideSupporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis.
- Supporting Information
-
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Reviews:
Total and formal synthesis of (–)-stemoamide:
Total synthesis of (±)-stemoamide:
Other synthetic studies towards stemoamide:
Recent synthetic studies on stemona alkaloids, see:
Asymmetric transfer hydrogenation (ATH):