Synthesis of (–)-Aspidophytine

Key words

Haplophyton cimicidum - (–)-aspidophytine - Stork–Danheiser transposition - Corey–Bakshi–Shibata reduction - Ireland–Claisen rearrangement - Malaprade–Lemieux–Johnson cleavage - iminium Hosomi–Sakurai reaction

Significance

The authors present the enantioselective synthesis of (–)-Aspidophytine, isolated from Haplophyton cimicidum leaves and used in Central America as an anticockroach and insecticide. Despite of remarkable achievements towards the synthesis of apsidospermine alkaloids, the complex structure of (–)-aspidophytine remained a challenge for more than 20 years.

Comment

The synthesis commences with the preparation of key intermediate H using a Corey–Bakshi–Shibata reduction followed by Ireland–Claisen rearrangement. Intermediates H and I are combined to form the pentacyclic core structure K in an iminium Hosomi–Sakurai reaction. The synthesis of (–)-aspidophytine is finished via lactonization and installation of the last remaining olefin.

Publication History

Article published online:
16 June 2023