P‐Stereogenic chiral phosphine BI‐BOP is employed for the first time as ligand to promote catalytic enantioselective synthesis of phosphoryl‐substituted atropisomeric vinylarenes through a palladium−carbene pathway. This strategy utilizes 10 mol% palladium(II) acetate, 10 mol% phosphine ligand as well as a variety of N‐tosylhydrazones and phosphoryl‐substituted aryl bromides as the reaction partners. The desired axially chiral vinylarenes were isolated with up to 80% yield and 96:4 er, and can be further converted effectively and stereoselectively into dialkylphosphoryl‐substituted atropisomeric arenes through a Grignard reaction. This protocol offers a general approach to synthesize phosphoryl‐substituted atropisomeric vinylarenes with high enantiomeric purities.

中文翻译：

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P-立体异构的手性膦-钯配合物催化磷酸取代的对映异构体乙烯基芳烃的对映选择性合成

P-Stereogenic手性膦BI-BOP首次用作配体，以通过钯-卡宾途径促进磷酰基取代的对映异构乙烯基芳烃的催化对映选择性合成。该策略利用10 mol％的乙酸钯（II），10 mol％的膦配体以及各种N-甲苯磺酰基hydr和磷酰基取代的芳基溴化物作为反应伙伴。分离所需的轴向手性乙烯基芳烃，收率高达80％和96：4 er，并可通过格氏反应进一步有效和立体选择性地转化为二烷基磷酰基取代的阻转异构体。该协议为合成具有高对映体纯度的磷酰基取代的阻转异构乙烯基芳烃提供了一种通用方法。