Catalytic Direct Hydrocarboxylation of Styrenes with CO and H

Overview

Journal Nat Commun

Specialty Biology

Date 2022 Dec 8

PMID 36481654

Authors

Yushu Jin

Joaquim Caner

Shintaro Nishikawa

Naoyuki Toriumi

Nobuharu Iwasawa

Affiliations

Soon will be listed here.

Abstract

A three-component hydrocarboxylation of an olefin with CO and H could be regarded as a dream reaction, since it would provide a straightforward approach for the synthesis of aliphatic carboxylic acids in perfect atom economy. However, this transformation has not been realized in a direct manner under mild conditions, because boosting the carboxylation with thermodynamically stable CO while suppressing the rapid hydrogenation of olefin remains a challenging task. Here, we report a rhodium-catalysed reductive hydrocarboxylation of styrene derivatives with CO and H under mild conditions, in which H served as the terminal reductant. In this approach, the carboxylation process was largely accelerated by visible light irradiation, which was proved both experimentally and by computational studies. Hydrocarboxylation of various kinds of styrene derivatives was achieved in good yields without additional base under ambient pressure of CO/H at room temperature. Mechanistic investigations revealed that use of a cationic rhodium complex was critical to achieve high hydrocarboxylation selectivity.

Citing Articles

Arylcarboxylation of unactivated alkenes with CO via visible-light photoredox catalysis.

Zhang W, Chen Z, Jiang Y, Liao L, Wang W, Ye J Nat Commun. 2023; 14(1):3529.

PMID: 37316537 PMC: 10267151. DOI: 10.1038/s41467-023-39240-8.

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