Zhao Shibin, Gensch Tobias, Murray Benjamin, Niemeyer Zachary L, Sigman Matthew S, Biscoe Mark R
Department of Chemistry, The City College of New York, 160 Convent Avenue, New York, NY 10031, USA.
Ph.D. Program in Chemistry, The Graduate Center of the City University of New York, 365 Fifth Avenue, New York, NY 10016, USA.
Science. 2018 Nov 9;362(6415):670-674. doi: 10.1126/science.aat2299. Epub 2018 Sep 20.
Despite the enormous potential for the use of stereospecific cross-coupling reactions to rationally manipulate the three-dimensional structure of organic molecules, the factors that control the transfer of stereochemistry in these reactions remain poorly understood. Here we report a mechanistic and synthetic investigation into the use of enantioenriched alkylboron nucleophiles in stereospecific Pd-catalyzed Suzuki cross-coupling reactions. By developing a suite of molecular descriptors of phosphine ligands, we could apply predictive statistical models to select or design distinct ligands that respectively promoted stereoinvertive and stereoretentive cross-coupling reactions. Stereodefined branched structures were thereby accessed through the predictable manipulation of absolute stereochemistry, and a general model for the mechanism of alkylboron transmetallation was proposed.
尽管利用立体专一性交叉偶联反应合理操控有机分子的三维结构具有巨大潜力，但控制这些反应中立体化学转移的因素仍未得到充分理解。在此，我们报告了一项关于对映体富集的烷基硼亲核试剂在立体专一性钯催化的铃木交叉偶联反应中的应用的机理和合成研究。通过开发一套膦配体的分子描述符，我们能够应用预测统计模型来选择或设计分别促进立体翻转和立体保持交叉偶联反应的不同配体。由此通过对绝对立体化学的可预测操控获得了立体定义的支链结构，并提出了烷基硼转金属化机理的通用模型。
