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Lithium Enolate with a Lithium-Alkyne Interaction in the Enantioselective Construction of Quaternary Carbon Centers: Concise Synthesis of (+)-Goniomitine.

ABSTRACT: We report a method for direct enantioselective alkylation of 3-alkynoic and 2,3-alkendioic acids that form quaternary stereogenic centers, and application of this method to the total enantioselective synthesis of a complex alkaloid (+)-goniomitine. The methods were effective in the alkylation of both 3-alkynoic acids, 2,3-alkendioic acids substrates with a broad range of heterocyclic and functionalized alkyl group substituents. Accompanying crystallographic studies provide mechanistic insight into the structure of well-defined chiral aggregates, highlighting cation-π interactions between lithium and alkyne groups.

SUBMITTER: Li Y

PROVIDER: S-EPMC9798608 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature

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Lithium Enolate with a Lithium-Alkyne Interaction in the Enantioselective Construction of Quaternary Carbon Centers: Concise Synthesis of (+)-Goniomitine.

Li Yang Y Paola Elena E Wang Zongheng Z Menard Gabriel G Zakarian Armen A

Angewandte Chemie (International ed. in English) 20221017 46

We report a method for direct enantioselective alkylation of 3-alkynoic and 2,3-alkendioic acids that form quaternary stereogenic centers, and application of this method to the total enantioselective synthesis of a complex alkaloid (+)-goniomitine. The methods were effective in the alkylation of both 3-alkynoic acids, 2,3-alkendioic acids substrates with a broad range of heterocyclic and functionalized alkyl group substituents. Accompanying crystallographic studies provide mechanistic insight in ...[more]

PMID: 36251869

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