Stitching two chiral centers with one catalyst.
Stitching two chiral centers with one catalyst.
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用一种催化剂缝合两个手性中心。
DOI：
10.1126/science.aba4222
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Watson,MaryP
中科院分区：
文献类型：
--
作者：
Xu,Jianyu;Watson,MaryP
过渡金属催化剂可以在亲电和(通常)亲核伙伴之间形成伴侣碳-碳(C-C)键。反应如以钯(Pd)为基础的铃木-宫浦交叉偶联竞争酰胺键的形成在使用频率上(1)。这种基于钯的交叉偶联与芳基-芳基偶联一样，加入了不饱和碳原子，但最近的许多努力都集中在烷基-烷基交叉偶联(2)。基于手性镍(Ni)的催化剂不仅能够有效地形成C-C键，而且能够控制亲电伙伴烷基上的立体中心的立体化学。类似的控制只对单环亲核配对进行了证明，这种亲核试剂也是选择性地在两个烷基片段上形成立体中心所需要的。在本期第559页上，Huoet al.(3)证明了单个手性镍催化剂可以连接两个烷基，并对相邻立体中心的取向进行高度控制。
Transition metal–based catalysts can chaperone carbon-carbon (C–C) bond formation between an electrophilic and a (usually) nucleophilic partner. Reactions such as the palladium (Pd)–based Suzuki–Miyaura cross-coupling rival amide-bond formation in frequency of use (1). Such Pd-based cross-couplings join unsaturated carbon atoms, as in aryl-aryl couplings, but many recent efforts have focused on alkyl-alkyl cross-couplings (2). Chiral nickel (Ni)–based catalysts have enabled both efficient C–C bond formation as well as control over the stereochemistry of a stereocenter on the electrophilic-partner alkyl group. Similar control has only been demonstrated for a single cyclic nucleophilic partner, and this nucleophile has also been needed for the selective formation of stereocenters on both alkyl fragments. On page 559 of this issue, Huoet al.(3) demonstrate that a single chiral Ni catalyst can join two alkyl groups with high levels of control over the orientations of the neighboring stereocenters.