Lee SangHyun, Yu Jianyang D, Monterde Alex L, Tung Sarah E, Wang Ya-Nong, Gay Brittany L, Hull Kami L
University of Texas at Austin, 100 East 24th Street, Austin, Texas, 78712, United States.
Department of Chemistry, University of Texas at Austin, 100 East 24 Street, Austin, Texas, 78712, United States.
ACS Catal. 2024 Sep 20;14(18):14242-14250. doi: 10.1021/acscatal.4c03955. Epub 2024 Sep 12.
We report a general cross-nucleophile alkene alkylarylation which adds two different boronic acids, an alkyl and an aryl, across a vinylarene to afford 1,1-diarylalkanes. The excellent chemoselectivity derives from the distinct reactivities of the two boronic acids: the alkylboronic acid is selectively oxidized to an alkyl radical while the arylboronic acid favors transmetalation with the Cu(II)-catalyst. Mechanistic studies suggest that Lewis acid-Lewis base interactions between generated boroxines and added amine are critical for selectivity. A scope of 37 examples is presented with structurally and electronically diverse alkyl, vinyl, and aryl coupling partners. The synthetic utility is demonstrated in the preparation of Pimozide and MCF-7 analogues.
我们报道了一种通用的交叉亲核试剂烯烃烷基芳基化反应，该反应可将两种不同的硼酸（一种烷基硼酸和一种芳基硼酸）加成到乙烯基芳烃上，生成1,1-二芳基烷烃。出色的化学选择性源于两种硼酸不同的反应活性：烷基硼酸被选择性氧化为烷基自由基，而芳基硼酸则倾向于与铜（II）催化剂进行转金属化反应。机理研究表明，生成的硼酸酯与添加的胺之间的路易斯酸-路易斯碱相互作用对选择性至关重要。本文展示了37个实例，涉及结构和电子性质多样的烷基、乙烯基和芳基偶联伙伴。该反应的合成实用性在匹莫齐特和MCF-7类似物的制备中得到了证明。
