Liu Jianzhong, Pan Jun, Luo Xiao, Qiu Xu, Zhang Cheng, Jiao Ning
State Key Laboratory of Natural and Biomimetic Drugs, Peking University, 100191 Beijing, China.
State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
Research (Wash D C). 2020 Nov 10;2020:7947029. doi: 10.34133/2020/7947029. eCollection 2020.
As a readily available feedstock, styrene with about 25 million tons of global annual production serves as an important building block and organic synthon for the synthesis of fine chemicals, polystyrene plastics, and elastomers. Thus, in the past decades, many direct transformations of this costless styrene feedstock were disclosed for the preparation of high-value chemicals, which to date, generally performed on the functionalization of styrenes through the allylic C-H bond, C( )-H bond, or the C=C double bond cleavage. However, the dealkenylative functionalization of styrenes via the direct C-C single bond cleavage is so far challenging and still unknown. Herein, we report the novel and efficient C-C amination and hydroxylation reactions of styrenes for the synthesis of valuable aryl amines and phenols via the site-selective C(Ar)-C(alkenyl) single bond cleavage. This chemistry unlocks the new transformation and application of the styrene feedstock and provides an efficient protocol for the late-stage modification of substituted styrenes with the site-directed dealkenylative amination and hydroxylation.
作为一种易于获取的原料，全球年产量约2500万吨的苯乙烯是合成精细化学品、聚苯乙烯塑料和弹性体的重要基石和有机合成子。因此，在过去几十年中，人们公开了许多利用这种低成本苯乙烯原料进行的直接转化反应，用于制备高价值化学品，迄今为止，这些反应通常是通过烯丙基C-H键、C( )-H键或C=C双键裂解来实现苯乙烯的官能化。然而，通过直接C-C单键裂解实现苯乙烯的脱烯基官能化目前仍具有挑战性，且尚不清楚。在此，我们报道了通过位点选择性C(Ar)-C(烯基)单键裂解合成有价值的芳基胺和酚的新型高效苯乙烯C-C胺化和羟基化反应。这种化学方法开启了苯乙烯原料的新转化和应用，并为通过位点导向的脱烯基胺化和羟基化对取代苯乙烯进行后期修饰提供了一种有效方法。
