Rhodium-Catalyzed Dynamic Kinetic [4+2] Cycloaddition of Allene-1,3-Dienes

Yulin Han; Anni Qin; Qian Zhang; Xue Zhang; Hui Qian; Shengming Ma

doi:10.1002/anie.202211635

Rhodium-Catalyzed Dynamic Kinetic [4+2] Cycloaddition of Allene-1,3-Dienes

Angew Chem Int Ed Engl. 2022 Nov 21;61(47):e202211635. doi: 10.1002/anie.202211635. Epub 2022 Oct 21.

Authors

Yulin Han¹, Anni Qin¹, Qian Zhang¹, Xue Zhang², Hui Qian¹, Shengming Ma^{1

2}

Affiliations

¹ Research Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan Lu, Shanghai, 200433, P. R. China.
² State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, P. R. China.

PMID: 36129393
DOI: 10.1002/anie.202211635

Abstract

Rh-catalyzed dynamic kinetic intramolecular [4+2] cycloaddition reaction of 1,3-disubstituted allene-1,3-dienes afforded cis-fused [4.3.0]bicyclic products with an excellent chemo-, diastereo-, and enantio-selectivity. Many synthetically useful functional groups are tolerated. The synthetic utility has been demonstrated. Based on the careful experimental studies, a mechanism involving the rapid racemization of the allene moiety in the starting materials has been proposed.

Keywords: Allenes; Asymmetric Catalysis; Cycloaddition; Rhodium.

Publication types

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

MeSH terms

Catalysis
Cycloaddition Reaction
Molecular Structure
Rhodium*
Stereoisomerism

Substances

propadiene
Rhodium