Rhodium‐Catalyzed Hydrocarboxylation of Olefins with Carbon Dioxide. Issue 19 (3rd May 2016)

• Record Type: Journal Article
• Authors: Kawashima, Shingo; Aikawa, Kohsuke; Mikami, Koichi
• Is Part Of: European journal of organic chemistry. Issue 19(2016)
• Page Start: 3166
• Page End: 3170
• Publication Date: 2016-05-03
• Subjects: Asymmetric catalysis -- Hydrocarboxylation -- Rhodium -- Hydrides -- Carboxylic acids; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201600338
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : The catalytic hydrocarboxylation of styrenes derivatives and α, β‐unsaturated carbonyl compounds with CO2 (101.3 kPa) in the presence of an air‐stable rhodium catalyst was explored. The combination of [RhCl(cod)]2 (cod = cyclooctadiene) as a catalyst and diethylzinc as a hydride source allowed for effective hydrocarboxylation and provided the corresponding α‐aryl carboxylic acids in moderate to excellent yields. In this catalytic process with carbon dioxide, intervention of the Rh I –H species, which could be generated from the Rh I catalyst and diethylzinc, was clarified. Significantly, the catalytic asymmetric hydrocarboxylation of α, β‐unsaturated esters with carbon dioxide was also performed by employing a cationic rhodium complex possessing ( S )‐(–)‐4, 4′‐bi‐1, 3‐benzodioxole‐5, 5′‐diylbis(diphenylphosphine) [( S )‐SEGPHOS] as a chiral diphosphine ligand. A plausible model for asymmetric induction was proposed by determination of the absolute configuration of the product. Abstract : The Rh‐catalyzed hydrocarboxylation of styrene derivatives and α, β‐unsaturated carbonyl compounds with CO2 is shown. The use of [RhCl(cod)]2 (cod = cyclooctadiene) as a catalyst and diethylzinc as a hydride source provides the corresponding α‐aryl carboxylic acids in moderate to excellent yields. Additionally, this catalyst system can be used in the asymmetric version of this reaction.