Catalytic asymmetric cationic shifts of aliphatic hydrocarbons

• 成果类型: Article
• 署名作者: Wakchaure, Vijay N.; DeSnoo, William; Laconsay, Croix J.; Leutzsch, Markus; Tsuji, Nobuya; Tantillo, Dean J.; List, Benjamin
• 署名单位: Max Planck Society; University of California System; University of California Davis; Hokkaido University
• 刊物名称: Nature
• ISSN/ISSBN: 0028-3872
• DOI: 10.1038/s41586-023-06826-7
• 发表日期: 2024-01-11
• 页码: 287-292
• 关键词: hydrogenation; activation; dispersion; balance; olefins

摘要

Asymmetric catalysis is an advanced area of chemical synthesis, but the handling of abundantly available, purely aliphatic hydrocarbons has proven to be challenging. Typically, heteroatoms or aromatic substructures are required in the substrates and reagents to facilitate an efficient interaction with the chiral catalyst. Confined acids have recently been introduced as tools for homogenous asymmetric catalysis, specifically to enable the processing of small unbiased substrates1. However, asymmetric reactions in which both substrate and product are purely aliphatic hydrocarbons have not previously been catalysed by such super strong and confined acids. We describe here an imidodiphosphorimidate-catalysed asymmetric Wagner-Meerwein shift of aliphatic alkenyl cycloalkanes to cycloalkenes with excellent regio- and enantioselectivity. Despite their long history and high relevance for chemical synthesis and biosynthesis, Wagner-Meerwein reactions utilizing purely aliphatic hydrocarbons, such as those originally reported by Wagner and Meerwein, had previously eluded asymmetric catalysis. We describe an imidodiphosphorimidate-catalysed asymmetric Wagner-Meerwein shift of aliphatic alkenyl cycloalkanes to cycloalkenes with excellent regio- and enantioselectivity.