Enantioselective Dearomative Cyclization Enabled by Asymmetric Cooperative Gold Catalysis
Enantioselective Dearomative Cyclization Enabled by Asymmetric Cooperative Gold Catalysis
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不对称协同金催化实现对映选择性脱芳香环化
DOI：
10.1002/anie.202207518
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Zhang, Liming
中科院分区：
文献类型：
--
作者：
Zhao, Ke;Kohnke, Philip;Yang, Ziguang;Cheng, Xinpeng;You, Shu‐Li;Zhang, Liming
金（I）催化的对映选择性脱芳构化通过金属-手性配体合作实现。开发了一种新的和发散的手性双官能联萘-2-基膦的合成方法，以允许快速获得这些配体，这反过来又促进了这种化学方法在广泛的底物范围内的应用，包括1-萘酚，2-萘酚和苯酚。通过底物和配体远程碱性基团之间的氢键键合，选择性加速一种对映体形成，实现了高达98%的对映体过量。DFT计算支持协同催化并证实了反应的立体化学结果。
A gold(I)‐catalyzed enantioselective dearomatization is achieved via metal‐chiral ligand cooperation. A new and divergent synthesis of chiral bifunctional binaphthyl‐2‐ylphosphines is developed to allow rapid access to these ligands, which in turn facilitate the application of this chemistry to a broad substrate scope including 1‐naphthols, 2‐naphthols, and phenols. Enantiomeric excesses up to 98 % are achieved via selective acceleration of one enantiomer formation enabled by hydrogen bonding between substrate and ligand remote basic group. DFT calculations lend support to the cooperative catalysis and substantiate the reaction stereochemical outcomes.