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Beilstein-Institut, Beilstein Journal of Organic Chemistry, (9), p. 2358-2366, 2013

DOI: 10.3762/bjoc.9.271

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Towards stereochemical control: A short formal enantioselective total synthesis of pumiliotoxins 251D and 237A

Journal article published in 2013 by Jie Zhang, Hong-Kui Zhang, Pei-Qiang Huang ORCID
This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

A concise enantioselective synthesis of the advanced intermediate 5 for the synthesis of pumiliotoxins (Gallagher’s intermediate) is described. The synthesis started from the regio- and trans-diastereoselective (dr = 98:2) reductive 3-butenylation of (R)-3-(tert-butyldimethylsilyloxy)glutarimide 14. After O-desilylation and Dess–Martin oxidation, the resulting keto-lactam 10 was subjected to a highly trans-stereoselective addition of the methylmagnesium iodide to give carbinol 11 as sole diastereomer. An efficient ring closure procedure consisting of ozonolysis and reductive dehydroxylation provided the indolizidine derivative 5, which completed the formal enantioselective total synthesis of pumiliotoxins 251D and 237A.