Total Synthesis of (-)-Rhodomollanol A

Jianhong Gao; Peirong Rao; Kaixiang Xu; Shuaifeng Wang; Yufei Wu; Chi He; Hanfeng Ding

doi:10.1021/jacs.0c00308

Total Synthesis of (-)-Rhodomollanol A

J Am Chem Soc. 2020 Mar 11;142(10):4592-4597. doi: 10.1021/jacs.0c00308. Epub 2020 Feb 28.

Authors

Jianhong Gao¹, Peirong Rao¹, Kaixiang Xu¹, Shuaifeng Wang¹, Yufei Wu¹, Chi He¹, Hanfeng Ding^{1

2}

Affiliations

¹ Department of Chemistry, Zhejiang University, Hangzhou 310058, China.
² Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, China.

PMID: 32093468
DOI: 10.1021/jacs.0c00308

Abstract

An asymmetric approach for the first total synthesis of (-)-rhodomollanol A, a highly oxidized diterpenoid, is described. The efficient synthetic strategy features three key transformations: (1) an oxidative dearomatization-induced (5 + 2) cycloaddition/pinacol-type 1,2-acyl migration cascade to build up the bicyclo[3.2.1]octane skeleton; (2) a retro-Dieckmann fragmentation/vinylogous Dieckmann cyclization cascade to assemble the bicyclo[3.3.0]octane subunit; and (3) a photo-Nazarov cyclization/intramolecular cycloetherification cascade to forge the 7-oxabicyclo[4.2.1]nonane core structure of the natural product.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Cycloaddition Reaction
Diterpenes / chemical synthesis*
Oxidation-Reduction
Stereoisomerism

Substances

Diterpenes