德国马克斯·普朗克研究所List, Benjamin团队报道了脂肪烃催化不对称阳离子转换。相关研究成果发表在2024年1月10日出版的《自然》。

不对称催化是化学合成的一个先进领域，但大量可用的纯脂族碳氢化合物的处理已被证明是具有挑战性的。通常，在底物和试剂中需要杂原子或芳香亚结构以促进与手性催化剂的有效相互作用。最近，限制酸被引入作为均相不对称催化的工具，特别是用于处理小的无偏底物。然而，底物和产物都是纯脂族烃的不对称反应以前没有被这种超强和受限的酸催化过。

该文中，研究人员描述了亚氨基二磷酰亚胺催化的脂族链烯基环烷烃，向具有优异区域和对映选择性的环烯烃的不对称Wagner-Meerwein转换。尽管Wagner–Meerwein反应历史悠久，与化学合成和生物合成高度相关，但利用纯脂族烃的Wagner-Meerwein-反应，如Wagner和Meerwein最初报道的反应，以前曾忽略了不对称催化。

附：英文原文

Title: Catalytic asymmetric cationic shifts of aliphatic hydrocarbons

Author: Wakchaure, Vijay N., DeSnoo, William, Laconsay, Croix J., Leutzsch, Markus, Tsuji, Nobuya, Tantillo, Dean J., List, Benjamin

Issue&Volume: 2024-01-10

Abstract: 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.

DOI: 10.1038/s41586-023-06826-7

Source: https://www.nature.com/articles/s41586-023-06826-7