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Development of an enantioselective route toward the Lycopodium alkaloids: total synthesis of lycopodine.

ABSTRACT: Synthesis of a C(15)-desmethyl tricycle core of lycopodine has been accomplished. Key steps in the synthetic sequence include organocatalytic, intramolecular Michael addition of a keto sulfone and a tandem 1,3-sulfonyl shift/Mannich cyclization to construct the tricyclic core ring system. Synthetic work toward this natural product family led to the development of N-(p-dodecylphenylsulfonyl)-2-pyrrolidinecarboxamide, an organocatalyst which facilitates enantioselective, intramolecular Michael additions. A detailed mechanistic discussion is provided for both the intramolecular Michael addition and the sulfone rearrangement. Finally, the application of these discoveries to the enantioselective total synthesis of alkaloid lycopodine is described.

SUBMITTER: Yang H

PROVIDER: S-EPMC2943527 | biostudies-literature | 2010 Aug

REPOSITORIES: biostudies-literature

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Development of an enantioselective route toward the Lycopodium alkaloids: total synthesis of lycopodine.

Yang Hua H Carter Rich G RG

The Journal of organic chemistry 20100801 15

Synthesis of a C(15)-desmethyl tricycle core of lycopodine has been accomplished. Key steps in the synthetic sequence include organocatalytic, intramolecular Michael addition of a keto sulfone and a tandem 1,3-sulfonyl shift/Mannich cyclization to construct the tricyclic core ring system. Synthetic work toward this natural product family led to the development of N-(p-dodecylphenylsulfonyl)-2-pyrrolidinecarboxamide, an organocatalyst which facilitates enantioselective, intramolecular Michael add ...[more]

PMID: 20586477

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