南方科技大学谭斌团队报道了不对称Heck反应对映选择性构建蒽基轴向手性。相关研究成果于2024年7月2日发表于国际一流学术期刊《美国化学会杂志》。

蒽基是一种有趣的结构单元，在各个领域都有广泛应用。

该项研究提出了一种新的方法，通过远程控制的不对称策略将轴向手性引入这种全碳核心骨架。利用钯催化的蒽在C10位具有两个不同取代基的外环双键的对映选择性Heck芳基化来实现这种转化。当蒽基骨架中没有杂原子手柄时，对P-中心手性配体的明智鉴定对于确保反应性和立体控制方面的竞争能力至关重要。

C10单取代和二取代的底物都与所建立的催化体系相容，并且以良好到高度的对映体控制制备了结构多样的蒽基框架。随后对所获得的产物进行衍生，产生了一系列有价值的中心和轴向手性分子，从而突出了这种化学的实用性。DFT计算揭示了催化机理，并为实验观察到的该反应的对映选择性的起源提供了见解。

附：英文原文

Title: Enantioselective Construction of Anthracenylidene-Based Axial Chirality by Asymmetric Heck Reaction

Author: Shi-Jiang He, Boming Shen, Lian-Zheng Zuo, Shao-Hua Xiang, Huan-Huan Liu, Peiyuan Yu, Bin Tan

Issue&Volume: July 2, 2024

Abstract: Anthracenylidene is an intriguing structural unit with potential in various fields. The study presents a novel approach to introducing axial chirality into this all-carbon core skeleton through a remotely controlled desymmetrization strategy. A palladium-catalyzed enantioselective Heck arylation of exocyclic double bond of anthracene with two distinct substituents at the C10 position is harnessed to realize such a transformation. The judicious identification of the P-centrally chiral ligand is pivotal to ensure the competitive competence in reactivity and stereocontrol when the heteroatom handle is absent from the anthracenylidene skeleton. Both C10 mono- and disubstituted substrates were compatible for the established catalytic system, and structurally diverse anthracenylidene-based frameworks were forged with good-to-high enantiocontrol. The subsequent derivatization of the obtained products yielded a valuable array of centrally and axially chiral molecules, thus emphasizing the practicality of this chemistry. DFT calculations shed light on the catalytic mechanism and provided insights into the origin of the experimentally observed enantioselectivity for this reaction.

DOI: 10.1021/jacs.4c04024

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c04024