Development of a Strategy for the Total Synthesis of Aspidosperma Alkaloids via the Cyclobutenone-Based PET-Initiated Cationic Radical-Driven [2+2]/Retro-Mannich Reaction

Jianyu Long; Rudong Liu; Xinpeng Mu; Zhilin Song; Zhongchao Zhang; Zhen Yang

doi:10.1021/acs.orglett.4c00540

Development of a Strategy for the Total Synthesis of Aspidosperma Alkaloids via the Cyclobutenone-Based PET-Initiated Cationic Radical-Driven [2+2]/Retro-Mannich Reaction

Org Lett. 2024 Apr 19;26(15):2960-2964. doi: 10.1021/acs.orglett.4c00540. Epub 2024 Apr 9.

Authors

Jianyu Long¹, Rudong Liu¹, Xinpeng Mu¹, Zhilin Song¹, Zhongchao Zhang¹, Zhen Yang^{1

2

3}

Affiliations

¹ State Key Laboratory of Chemical Oncogenomics, Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055, China.
² Shenzhen Bay Laboratory, Shenzhen 518132, China.
³ Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education and Beijing National Laboratory for Molecular Science (BNLMS) and Peking-Tsinghua Center for Life Sciences, Peking University, Beijing 100871, China.

PMID: 38592965
DOI: 10.1021/acs.orglett.4c00540

Abstract

A novel strategy for the synthesis of Aspidosperma alkaloids has been achieved via a photoredox-initiated [2+2]/retro-Mannich reaction of tryptamine-substituted enaminones as a key step. The developed chemistry has been applied to the construction of the core tetracycle of Aspidosperma alkaloids (±)-aspidospermidine and (±)-limaspermidine.