清华大学李必杰团队报道了酰胺引导铑催化非环四取代烯烃的高对映选择性硼氢化反应。相关研究成果发表在2024年6月4日出版的国际学术期刊《美国化学会杂志》。

尽管在过去的几十年里，二取代和三取代烯烃的对映选择性硼氢化已经取得了进展，但自20世纪50年代以来，具有高非对映选择性和对映选择性的四取代烯烃的对映选择性硼化，仍然是一个未得到满足的挑战，因为其反应性极低，并且难以同时控制四取代烯的区域选择性和立体选择性。

该文中，研究人员报道了不同无环四取代烯烃的高度区域选择性、非对映选择性和对映选择性催化硼氢化反应。富含电子的铑络合物和配位助剂的微妙相互作用形成了一种高度适应性的催化剂，它有效地克服了低反应性并控制了立体选择性。催化剂体系的通用性体现在其对具有不同空间和电子性质的各种四取代烯烃的功效上。

附：英文原文

Title: Rhodium-Catalyzed Highly Enantioselective Hydroboration of Acyclic Tetrasubstituted Alkenes Directed by an Amide

Author: Hou-Xiang Lu, Cheng Wang, Tao-Tao Gao, En-Ze Lin, Shou-Lin Lu, Xin Hong, Bi-Jie Li

Issue&Volume: June 4, 2024

Abstract: Although progress has been made in enantioselective hydroboration of di- and trisubstituted alkenes over the past decades, enantioselective hydroboration of tetrasubstituted alkenes with high diastereo- and enantioselectivities continues as an unmet challenge since the 1950s due to its extremely low reactivity and the difficulties to simultaneously control the regio- and stereoselectivity of a tetrasubstituted alkene. Here, we report highly regio-, diastereo-, and enantioselective catalytic hydroboration of diverse acyclic tetrasubstituted alkenes. The delicate interplay of an electron-rich rhodium complex and coordination-assistance forms a highly adaptive catalyst that effectively overcomes the low reactivity and controls the stereoselectivity. The generality of the catalyst system is exemplified by its efficacy across various tetrasubstituted alkenes with diverse steric and electronic properties.

DOI: 10.1021/jacs.4c04108

Source: https://pubs.acs.org/doi/full/10.1021/jacs.4c04108