Remote proton elimination: C-H activation enabled by distal acidification

• 成果类型: Article
• 署名作者: Grant, Phillip S.; Vavrik, Milos; Porte, Vincent; Meyrelles, Ricardo; Maulide, Nuno
• 署名单位: University of Vienna; University of Vienna
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-9798
• DOI: 10.1126/science.adi8997
• 发表日期: 2024-05-17
• 页码: 815-820
• 关键词: bond functionalization; hydrogen-exchange; cyclodecyl cation; super acids; reactivity; chemistry; alkanes; ions; polycondensation; intermediacy

摘要

Generally, the acidity of carbon-hydrogen bonds is most sensitive to functionality just one or two bonds away. Here, we present an approach to the formation of carbon-carbon sigma bonds by remote proton elimination, a distinct mode of carbon-hydrogen activation enabled by distal acidification through five carbon-carbon bonds. Application of remote proton elimination to cyclodecyl cations unveiled an appealing method for the synthesis of decalins. The transformation is regioconvergent, proceeds without the need for a directing group or precious metal, and demonstrates exquisite site selectivity. An in-depth computational study illuminated the reaction mechanism. Additionally, we describe the complete stereoisomeric enrichment of the decalin products through epimerization mediated by hydrogen atom transfer.