Shi-Jiang He, Boming Shen, Lian-Zheng Zuo, Shao-Hua Xiang*, Huan-Huan Liu, Peiyuan Yu* and Bin Tan*,
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引用次数: 0
摘要
亚蒽是一种有趣的结构单元,在各个领域都具有潜力。本研究提出了一种新方法,通过遥控去对称化策略将轴向手性引入这种全碳核心骨架。在钯催化下,蒽的外环双键在 C10 位置上有两个不同的取代基,通过对映选择性 Heck 芳基化反应实现了这种转化。当蒽基骨架上没有杂原子柄时,要确保反应活性和立体控制的竞争能力,明智地确定 P 中心手性配体至关重要。C10 单取代和二取代底物都能与所建立的催化系统兼容,并以良好甚至较高的对映体控制能力锻造出结构多样的亚蒽基框架。随后对获得的产物进行衍生,得到了一系列有价值的中心和轴向手性分子,从而强调了这种化学方法的实用性。DFT 计算揭示了这一反应的催化机理,并为实验观察到的对映体选择性的起源提供了见解。
Enantioselective Construction of Anthracenylidene-Based Axial Chirality by Asymmetric Heck Reaction
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.
期刊介绍:
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