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

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.

SUBMITTER: Zhang J

PROVIDER: S-EPMC3869269 | biostudies-literature | 2013

REPOSITORIES: biostudies-literature

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

Zhang Jie J Zhang Hong-Kui HK Huang Pei-Qiang PQ

Beilstein journal of organic chemistry 20131105

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 diaster ...[more]

PMID: 24367400

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