Enantioselective Total Synthesis and Absolute Configuration Assignment of (+)-Toxicodenane A

Xu-Long Qin; Guo-Jie Wu; Fu-She Han

doi:10.1021/acs.orglett.1c03293

Enantioselective Total Synthesis and Absolute Configuration Assignment of (+)-Toxicodenane A

Org Lett. 2021 Nov 5;23(21):8570-8574. doi: 10.1021/acs.orglett.1c03293. Epub 2021 Oct 15.

Authors

Xu-Long Qin^{1

2}, Guo-Jie Wu^{1

3}, Fu-She Han^{1

2}

Affiliations

¹ Key Lab of Synthetic Rubber, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 5625 Renmin Street, Changchun, Jilin 130022, China.
² University of Science and Technology of China, Hefei, Anhui 230026, China.
³ Key Lab of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.

PMID: 34652928
DOI: 10.1021/acs.orglett.1c03293

Abstract

We present the first enantioselective total synthesis and absolute configuration assignment of (+)-toxicodenane A via a nine-step sequence from the readily available material. The synthesis features a desymmetric enantioselective reduction of 2,2-disubstituted 1,3-cyclohexanedione for the synthesis of a chiral 2,2-disubstituted 3-hydroxy cyclohexanone building block, a highly diastereoselective Grignard reaction for the incorporation of an allyl group, and a Lewis acid-mediated intramolecular transacetalation and Prins cascade reaction for the construction of oxa-bridged bicyclic rings.

Publication types

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