当前位置: X-MOL 学术Nat. Chem. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
A site-selective amination catalyst discriminates between nearly identical C-H bonds of unsymmetrical disubstituted alkenes.
Nature Chemistry ( IF 19.2 ) Pub Date : 2020-06-15 , DOI: 10.1038/s41557-020-0470-z
Honghui Lei 1 , Tomislav Rovis 1
Affiliation  

C–H activation reactions enable chemists to unveil new retrosynthetic disconnections and streamline conventional synthetic approaches. A long-standing challenge in C–H activation is the inability to distinguish electronically and sterically similar C–H bonds. Although numerous synergistic combinations of transition-metal complexes and chelating directing groups have been utilized to distinguish C–H bonds, undirected regioselective C–H functionalization strategies remain elusive. Here we report a regioselective C–H activation/amination reaction of various unsymmetrical dialkyl-substituted alkenes. The regioselectivity of C–H activation is correlated to the electronic properties of allylic C–H bonds indicated by the corresponding 1JCH coupling constants. A linear relationship between the difference in the 1JCH coupling constants of the two competing allylic C–H bonds (Δ1JCH) and the C–H activation barriers (ΔΔG) has also been determined.



中文翻译:


位点选择性胺化催化剂可区分不对称二取代烯烃的几乎相同的 CH 键。



C-H 活化反应使化学家能够揭示新的逆合成断开并简化传统的合成方法。 C-H 活化的一个长期挑战是无法区分电子和空间相似的 C-H 键。尽管过渡金属配合物和螯合导向基团的多种协同组合已被用来区分 C-H 键,但无向区域选择性 C-H 官能化策略仍然难以捉摸。在这里,我们报道了各种不对称二烷基取代的烯烃的区域选择性C-H活化/胺化反应。 C-H 活化的区域选择性与烯丙基 C-H 键的电子性质相关,由相应的1 J CH耦合常数表示。两个竞争烯丙基 C-H 键的1 J CH耦合常数之差 (Δ 1 J CH ) 与 C-H 活化势垒 (ΔΔ G ) 之间的线性关系也已确定。

更新日期:2020-06-15
down
wechat
bug