{"title":"Catalytic Regio- and Enantioselective Remote Hydrocarboxylation of Unactivated Alkenes with CO<sub>2</sub>.","authors":"Li Zhou, Liping Li, Sudong Zhang, Xiao-Kang Kuang, You-Yun Zhou, Yong Tang","doi":"10.1021/jacs.4c05217","DOIUrl":null,"url":null,"abstract":"<p><p>The catalytic regio- and enantioselective hydrocarboxylation of alkenes with carbon dioxide is a straightforward strategy to construct enantioenriched α-chiral carboxylic acids but remains a big challenge. Herein we report the first example of catalytic highly enantio- and site-selective remote hydrocarboxylation of a wide range of readily available unactivated alkenes with abundant and renewable CO<sub>2</sub> under mild conditions enabled by the SaBOX/Ni catalyst. The key to this success is utilizing the chiral SaBOX ligand, which combines with nickel to simultaneously control both chain-walking and the enantioselectivity of carboxylation. This process directly furnishes a range of different alkyl-chain-substituted or benzo-fused α-chiral carboxylic acids bearing various functional groups in high yields and regio- and enantioselectivities. Furthermore, the synthetic utility of this methodology was demonstrated by the concise synthesis of the antiplatelet aggregation drug (<i>R</i>)-indobufen from commercial starting materials.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.4c05217","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The catalytic regio- and enantioselective hydrocarboxylation of alkenes with carbon dioxide is a straightforward strategy to construct enantioenriched α-chiral carboxylic acids but remains a big challenge. Herein we report the first example of catalytic highly enantio- and site-selective remote hydrocarboxylation of a wide range of readily available unactivated alkenes with abundant and renewable CO2 under mild conditions enabled by the SaBOX/Ni catalyst. The key to this success is utilizing the chiral SaBOX ligand, which combines with nickel to simultaneously control both chain-walking and the enantioselectivity of carboxylation. This process directly furnishes a range of different alkyl-chain-substituted or benzo-fused α-chiral carboxylic acids bearing various functional groups in high yields and regio- and enantioselectivities. Furthermore, the synthetic utility of this methodology was demonstrated by the concise synthesis of the antiplatelet aggregation drug (R)-indobufen from commercial starting materials.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.