Ligand-Controlled Nickel-Catalyzed Regiodivergent Cross-Electrophile Alkyl-Alkyl Couplings of Alkyl Halides.
Ligand-Controlled Nickel-Catalyzed Regiodivergent Cross-Electrophile Alkyl-Alkyl Couplings of Alkyl Halides.
复制标题
配体控制的镍催化的烷基卤化物的区域发散交叉亲电性烷基-烷基偶联。
DOI：
10.1002/anie.202215779
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发表时间：
2022
影响因子：
--
通讯作者：
W. Shu
中科院分区：
文献类型：
--
作者：
Wenfang Zhao;Huan Meng;Jia;W. Shu
在饱和烷基分子上的特定位置官能化是合成化学中的关键挑战。在此，通过Ni催化的烷基-烷基交叉亲电试剂偶联与第二个烷基溴的配体控制的不同位置的烷基化反应已经发展。该反应以受控的方式对一种烷基溴进行位点选择性异构化，提供了在烷基溴不同位点上可切换地获得不同烷基化结构的途径。该反应发生在三个相似的位置，具有优异的化学选择性和区域选择性，代表了显着的配体之间的烷基-烷基交叉偶联和镍迁移沿着烃侧链调谐反应。该反应提供了一个催化平台，以不同的饱和结构的烷基-烷基键的形成从相同的起始材料。
Functionalizing specific positions on a saturated alkyl molecule is a key challenge in synthetic chemistry. Herein, a ligand-controlled regiodivergent alkylations of alkyl bromides at different positions by Ni-catalyzed alkyl-alkyl cross-electrophile coupling with the second alkyl bromides has been developed. The reaction undergoes site-selective isomerization on one alkyl bromides in a controlled manner, providing switchable access to diverse alkylated structures at different sites of alkyl bromides. The reaction occurs at three similar positions with excellent chemo- and regioselectivity, representing a remarkable ligand tuned reactivity between alkyl-alkyl cross-coupling and nickel migration along the hydrocarbon side chain. This reaction offers a catalytic platform to diverse saturated architectures by alkyl-alkyl bond-formation from identical starting materials.