☆ 4.7 Article

Protecting-Group-Free Formal Synthesis of Aspidospermidine: Ring-Opening Cyclization of Spirocyclopropane with Amine Followed by Regioselective Alkylations

JOURNAL OF ORGANIC CHEMISTRY (2019)

Journal

JOURNAL OF ORGANIC CHEMISTRY

Volume 84, Issue 24, Pages 15990-15996

Publisher

AMER CHEMICAL SOC

DOI: 10.1021/acs.joc.9b02469

Keywords

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Categories

Chemistry, Organic

Funding

Ministry of Education, Culture, Sports, Science and Technology, Japan [18K05119]
Grants-in-Aid for Scientific Research [18K05119] Funding Source: KAKEN

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Abstract

A concise formal synthesis of (+/-)-aspidospermidine via Stork's intermediate, which could be used as a divergent synthesis of Aspidosperma alkaloids, was achieved by employing a ring-opening cyclization of spirocyclopropane with amine followed by a regioselective intramolecular/intermolecular alkylation sequence. Stork's intermediate was synthesized in only six steps from a simple starting material, 1,3-cyclohexanedione, and was converted into (+/-)-aspidospermidine. To the best of our knowledge, this synthesis of Stork's intermediate involves the least number of steps to date. Furthermore, no protecting groups were used during this synthesis.

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