Asymmetric Suzuki–Miyaura cross-couplings with aryl boronic acids and allylic electrophiles are a powerful method to convert racemic mixtures into enantioenriched products. Currently, enantioconvergent allylic arylations are limited to substrates that are symmetrical about the allylic unit, and the absence of strategies to control regio-, E/Z- and enantioselectivity in acyclic allylic systems is a major restriction. Here, using a system capable of either conjugate addition or allylic arylation, we have discovered the structural features and experimental conditions that allow an acyclic system to undergo chemo- and regioselective, enantioconvergent allylic Suzuki–Miyaura-type arylation. A wide variety of boronic acid coupling partners can be used, and both alkyl and aromatic substituents are tolerated on the allylic unit so that a wide variety of structures can be obtained. Preliminary mechanistic studies reveal that the chelating ability of the ester group is crucial to obtaining high regio- and enantioselectivity. Using this method, we were able to synthesize the natural products (S)-curcumene and (S)-4,7-dimethyl-1-tetralone and the clinically used antidepressant sertraline (Zoloft).

与芳基硼酸和烯丙基亲电子试剂的不对称铃木-宫浦交叉偶联是将外消旋混合物转化为对映体富集产物的有效方法。目前，对映体烯丙基芳基化仅限于关于烯丙基单元对称的底物，并且缺乏控制无环烯丙基系统中的区域选择性、E / Z-和对映选择性的策略是主要限制。在这里，使用能够进行共轭加成或烯丙基芳基化的系统，我们发现了允许无环系统进行化学和区域选择性、对映体收敛的烯丙基铃木-宫浦型芳基化的结构特征和实验条件。可以使用多种硼酸偶联配对物，并且烯丙基单元上允许烷基和芳香族取代基，从而可以获得多种结构。初步机理研究表明，酯基的螯合能力对于获得高区域选择性和对映选择性至关重要。利用该方法，我们能够合成天然产物( S )-姜黄烯和( S )-4,7-二甲基-1-四氢萘酮以及临床使用的抗抑郁药舍曲林(Zoloft)。