Rhodium-Catalyzed Desymmetrization by Hydroformylation of Cyclopentenes: Synthesis of Chiral Carbocyclic Nucleosides

Cai You; Biao Wei; Xiuxiu Li; Yusheng Yang; Yue Liu; Hui Lv; Xumu Zhang

doi:10.1002/anie.201601478

Rhodium-Catalyzed Desymmetrization by Hydroformylation of Cyclopentenes: Synthesis of Chiral Carbocyclic Nucleosides

Angew Chem Int Ed Engl. 2016 May 23;55(22):6511-4. doi: 10.1002/anie.201601478. Epub 2016 Apr 18.

Authors

Cai You¹, Biao Wei¹, Xiuxiu Li¹, Yusheng Yang¹, Yue Liu¹, Hui Lv², Xumu Zhang³

Affiliations

¹ Key Laboratory of Biomedical Polymers of Ministry of Education & College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei, 430072, China.
² Key Laboratory of Biomedical Polymers of Ministry of Education & College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei, 430072, China. huilv@whu.edu.cn.
³ Key Laboratory of Biomedical Polymers of Ministry of Education & College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei, 430072, China. xumu@whu.edu.cn.

PMID: 27086543
DOI: 10.1002/anie.201601478

Abstract

Excellent enantioselectivities (up to 97 % ee) and diastereoselectivities (up to >99:1 d.r.) have been achieved in the desymmetrization of cyclopentenes by catalytic hydroformylation. This novel methodology provides an efficient and concise synthetic route to chiral cyclopentane carboxaldehydes. The key intermediate, (1S,3S)-(3-hydroxymethyl)cyclopentanol, for the synthesis of carbocyclic-ddA was obtained in three steps.

Keywords: alkenes; diastereoselectivity; enantioselectivity; hydroformylation; rhodium.

Publication types

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