Nickel-Catalyzed Chemodivergent 1,1-Difunctionalization of Unactivated α-Olefins with Alkynyl Electrophiles and B2pin2
Nickel-Catalyzed Chemodivergent 1,1-Difunctionalization of Unactivated α-Olefins with Alkynyl Electrophiles and B2pin2
复制标题
镍催化未活化 α-烯烃与炔基亲电子试剂和 B2pin2 的化学发散 1,1-双官能化
DOI：
10.1021/acscatal.0c00898
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发表时间：
2020-05-01
期刊：
影响因子：
12.9
通讯作者：
Yin, Guoyin
中科院分区：
文献类型：
--
作者：
Li, Yangyang;Wei, Hong;Yin, Guoyin
发散催化代表了增加分子复杂性和探索有机合成催化模式的强大策略。在此，我们报道了镍催化、化学发散的未活化α-烯烃的1,1-炔基硼化反应和1,1-二炔基化反应。该研究不仅为炔丙硼酸酯和偕二炔基烷烃的发散合成提供了一种高效、模块化的方案，而且实现了Ni/B双金属中间体的可控、单或双交叉偶联。机理研究表明，二硼试剂（B-2 pin(2)）在二炔化反应中发挥着重要作用，既充当还原剂又充当瞬时辅助基团。值得注意的是，这两种反应均表现出高区域选择性和良好的官能团耐受性。此外，产品的综合价值已通过多次下游改造得到证明。
Divergent catalysis represents a powerful strategy for increasing molecular complexity and exploring catalytic modes in organic synthesis. Herein, we report, a nickel-catalyzed, chemodivergent 1,1-alkynylboration, and 1,1-dialkynylation of unactivated alpha-olefins. This study not only provides an efficient and modular protocol for the divergent synthesis of propargylic boronic esters and gem-dialkynylalkanes, but also achieves a controllable, single or double cross-coupling of Ni/B bimetallic intermediates. Mechanistic studies reveal that the diboron reagent (B-2 pin(2)) plays a significant role in the dialkynylation reaction, serving as both the reductant and transient assisting group. Notably, both reactions show high regioselectivities and good functional group tolerance. In addition, the synthetic value of the products has been demonstrated with several downstream transformations.