Work

Stereoselective rhodium-catalyzed reaction of allenes with organoboronic reagents for diversified branched 1,3-alkadienes

Year: 2024

Type: article

Abstract: The terminal isoprene unit, as the simplest branched 1,3-diene unit, exists in a wide range of natural products and bioactive molecules. Herein, we report a stereoselective rhodium-catalyzed reaction of allenes with readily available methyl pinacol boronic ester, providing a straightforward approach to isoprene derivatives with a very high E-stereoselectivity. Its synthetic potential has been illustrated by a concise synthesis of natural product schinitrienin. Such a protocol can be easily extended to aryl and alkenyl boronic reagents affording 2-aryl or -alkenyl substituted 1,3-dienes, which are also of high importance in organic synthesis but remain challenging for their selective synthesis, with a remarkable stereoselectivity. A series of deuterium-labeling experiments indicate a unique mechanism, which involves reversible β-H elimination as well as hydrometalation and isomerization of the allylic rhodium species.

Source: Nature Communications

DOI: 10.1038/s41467-024-52209-5

Authors: Weiyi Wang, Shichao Hong, Wenxiang He, Xue Zhang, Hui Qian, Shengming Ma

Institutions: Fudan University, Chinese Academy of Sciences, Shanghai Institute of Organic Chemistry, State Key Laboratory of Organometallic Chemistry

Language: English

Topic: Catalytic Alkyne Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: gold

Estimated APC paid: $6,790

Funders: National Natural Science Foundation of China, Shanghai Rising-Star Program