南方科技大学谭斌团队报道了有机催化剂控制的位置选择性芳烃C–H功能化的策略。相关研究成果发表在2021年8月9日出版的《自然—化学》。

在过去的三十年中，有机催化已经成为一个强大的催化平台，并逐渐被纳入常规的合成工具箱以获得手性分子。然而，它其在非活性芳基C–H键的位置和对映选择性功能化中的应用仍处于起步阶段。

该文中，研究人员提出了一种有机催化剂控制的对选择性芳烃C–H功能化策略来解决该问题，其仍然是芳烃功能化化学中一个长久的挑战。通过模拟酶催化，手性磷酸催化剂为立体诱导提供了一个理想的手性环境，突出的取代基可以控制化学选择性和位置选择性。各种类型的亲核试剂与该方法兼容，在可行的分子环境中提供100多种具有立体确定的碳中心或轴的对位选择性加合物。

该方案有望为芳烃C–H键的可控对位选择性官能化提供一种通用策略。

附：英文原文

Title: Organocatalyst-controlled site-selective arene C–H functionalization

Author: Mao, Jian-Hui, Wang, Yong-Bin, Yang, Limin, Xiang, Shao-Hua, Wu, Quan-Hao, Cui, Yuan, Lu, Qian, Lv, Jie, Li, Shaoyu, Tan, Bin

Issue&Volume: 2021-08-09

Abstract: Over the past three decades, organocatalysis has emerged as a powerful catalysis platform and has gradually been incorporated into the routine synthetic toolbox to obtain chiral molecules. However, its application in the site- and enantioselective functionalization of inactive aryl C–H bonds remains in its infancy. Here, we present an organocatalyst-controlled para-selective arene C–H functionalization strategy that addresses this issue, which remains an enduring challenge in arene functionalization chemistry. By emulating enzyme catalysis, the chiral phosphoric acid catalyst offers an ideal chiral environment for stereoinduction, and the projecting substituents give control of chemo- and site-selectivity. Various types of nucleophile are compatible with this method, affording more than 100 para-selective adducts with stereodefined carbon centres or axes in viable molecular contexts. This protocol is expected to provide a general strategy for para-selective functionalization of arene C–H bonds in a controlled manner.

DOI: 10.1038/s41557-021-00750-x

Source: https://www.nature.com/articles/s41557-021-00750-x