Total Synthesis of Penicibilaenes Enabled by a Tandem Double Conia-ene Type Reaction

Zheyuan Wang; Zhilin Song; Jun Huang; Zhen Yang

doi:10.1021/jacs.3c14614

Total Synthesis of Penicibilaenes Enabled by a Tandem Double Conia-ene Type Reaction

J Am Chem Soc. 2024 Feb 21;146(7):4363-4368. doi: 10.1021/jacs.3c14614. Epub 2024 Feb 8.

Authors

Zheyuan Wang¹, Zhilin Song¹, Jun Huang², Zhen Yang^{1

3

4}

Affiliations

¹ State Key Laboratory of Chemical Oncogenomics and Key Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School, Shenzhen 518055, China.
² School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China.
³ Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Beijing National Laboratory for Molecular Science and Peking-Tsinghua Center for Life Sciences, Peking University, Beijing 100871, China.
⁴ Shenzhen Bay Laboratory, Shenzhen 518055, China.

PMID: 38329963
DOI: 10.1021/jacs.3c14614

Abstract

The total syntheses of penicibilaenes A and B are described. The key step is the ^tBuOK/DMSO-mediated tandem 5-exo-dig Conia-ene type reaction and 6-exo-dig Conia-ene type reaction to install the tricyclic [6.3.1.0^1,5] dodecane core of penicibilaenes from dibutynyl cyclohexanone in a single step, together with a sequence of copper-mediated conjugate addition and Crabtree's hydrogenation to forge the stereogenic centers at C5 and C2, respectively.