The staying power of electron-poor ligands The venerable Suzuki coupling reaction originally used palladium to pair up unsaturated carbon centers. The protocol has been widely extended to chiral saturated alkyl carbons, but control over product stereochemistry is a pressing challenge. Zhao et al. systematically studied how the properties of the phosphine ligands that are coordinated to the catalyst influence the stereochemical outcome. Certain electron-withdrawing phosphines favored retention of the initial configuration in chiral alkyltrifluoroborate reactants. Conversely, bulky electron-rich phosphines lead to inverted configurations in the products. Science, this issue p. 670 Electron-withdrawing phosphine ligands promote stereochemical retention in Suzuki coupling of chiral borates with arenes. 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.

中文翻译：

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通过配体参数化实现对映体 Pd 催化的 C-C 键形成

缺电子配体的持久力 古老的 Suzuki 偶联反应最初使用钯来配对不饱和碳中心。该协议已广泛扩展到手性饱和烷基碳，但对产品立体化学的控制是一项紧迫的挑战。赵等人。系统地研究了与催化剂配位的膦配体的性质如何影响立体化学结果。某些吸电子膦有利于在手性烷基三氟硼酸盐反应物中保留初始构型。相反，笨重的富电子膦会导致产品中的倒置构型。科学，这个问题 p。670 吸电子膦配体在手性硼酸盐与芳烃的 Suzuki 偶联中促进立体化学保留。尽管使用立体特异性交叉偶联反应合理操纵有机分子的三维结构具有巨大的潜力，但在这些反应中控制立体化学转移的因素仍然知之甚少。在这里，我们报告了在立体定向 Pd 催化的 Suzuki 交叉偶联反应中使用对映体富集的烷基硼亲核试剂的机械和合成研究。通过开发一套膦配体的分子描述符，我们可以应用预测统计模型来选择或设计不同的配体，分别促进立体反转和立体保留交叉偶联反应。从而通过绝对立体化学的可预测操作获得立体定义的支化结构，