Selective 1,2‐Hydroarylation(Alkenylation) of gem‐Difluoroalkenes to Access (−CF2H) Motifs

Author:

Lin Leroy Qi Hao1,Rentería‐Gómez Ángel2,Martin Robert T.3,Zhang Ying‐Qi1,Ong Kelvin Zhi Wei1,Parris Adam B.1,Gutierrez Osvaldo2,Koh Ming Joo1ORCID

Affiliation:

1. Department of Chemistry National University of Singapore 4 Science Drive 2 Singapore 117544 Singapore

2. Department of Chemistry Texas A&M University College Station TX 77843 USA

3. Department of Chemistry and Biochemistry University of Maryland College Park MD 20742 USA

Abstract

AbstractAn emerging class of C−C coupling transformations that furnish drug‐like building blocks involves catalytic hydrocarbonation of alkenes. However, despite notable advances in the field, hydrocarbon addition to gem‐difluoroalkenes without additional electronic activation remains largely unsuccessful. This owes partly to poor reactivity and the propensity of difluoroalkenes to undergo defluorinative side reactions. Here, we report a nickel catalytic system that promotes efficient 1,2‐selective hydroarylation and hydroalkenylation, suppressing defluorination and providing straightforward access to a diverse assortment of prized organofluorides bearing difluoromethyl‐substituted carbon centers. In contrast to radical‐based pathways and reactions triggered by hydrometallation via a nickel‐hydride complex, our experimental and computational studies support a mechanism in which a catalytically active nickel‐bromide species promotes selective carbonickelation with difluoroalkenes followed by alkoxide exchange and hydride transfer, effectively overcoming the difluoroalkene's intrinsic electronic bias.

Funder

Ministry of Education - Singapore

National Institutes of Health

Welch Foundation

Publisher

Wiley

Subject

General Medicine

同舟云学术

1.学者识别学者识别

2.学术分析学术分析

3.人才评估人才评估

"同舟云学术"是以全球学者为主线,采集、加工和组织学术论文而形成的新型学术文献查询和分析系统,可以对全球学者进行文献检索和人才价值评估。用户可以通过关注某些学科领域的顶尖人物而持续追踪该领域的学科进展和研究前沿。经过近期的数据扩容,当前同舟云学术共收录了国内外主流学术期刊6万余种,收集的期刊论文及会议论文总量共计约1.5亿篇,并以每天添加12000余篇中外论文的速度递增。我们也可以为用户提供个性化、定制化的学者数据。欢迎来电咨询!咨询电话:010-8811{复制后删除}0370

www.globalauthorid.com

TOP

Copyright © 2019-2024 北京同舟云网络信息技术有限公司
京公网安备11010802033243号  京ICP备18003416号-3