Engaging Sulfonamides: Intramolecular Cross-Electrophile Coupling Reaction of Sulfonamides with Alkyl Chlorides
Engaging Sulfonamides: Intramolecular Cross-Electrophile Coupling Reaction of Sulfonamides with Alkyl Chlorides
复制标题
磺酰胺的参与：磺酰胺与烷基氯的分子内交叉电偶联反应
DOI：
10.1021/acs.joc.9b02603
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发表时间：
2020
影响因子：
3.6
通讯作者：
Jarvo Elizabeth R.
中科院分区：
文献类型：
--
作者：
Lucas Erika L.;Hewitt Kirsten A.;Chen Pan-Pan;Castro Anthony J.;Hong Xin;Jarvo Elizabeth R.
由于C-N键的固有强度，胺衍生物作为偶联伴侣的应用是罕见的。本文报道了无张力苄基磺酰胺类化合物的首次交叉亲电偶联反应。镍催化的无环和环状苄基磺酰胺与侧链烷基氯的分子内交叉亲电偶联反应生成环丙烷产物。机理实验和DFT计算与碘化镁加速苄基磺酰胺的氧化加成反应的引发是一致的。这项工作建立了中性和无张力的胺衍生物作为XEC的合作伙伴，取代结构重排的苄基磺酰胺，并提供了有价值的信息，催化剂设计的发展新的交叉亲电偶联反应的碳-杂原子键。
The application of amine derivatives as coupling partners is rare due to the inherent strength of the C–N bond. Herein, we report the first cross-electrophile coupling reaction of unstrained benzylic sulfonamides. Nickel-catalyzed intramolecular cross-electrophile coupling reactions of acyclic and cyclic benzylic sulfonamides with pendant alkyl chlorides generate cyclopropane products. Mechanistic experiments and DFT calculations are consistent with initiation of the reaction by magnesium iodide accelerated oxidative addition of the benzylic sulfonamide. This work establishes neutral and unstrained amine derivatives as XEC partners, furnishes structural rearrangement of benzylic sulfonamides, and provides valuable information regarding catalyst design for the development of new cross-electrophile coupling reactions of carbon–heteroatom bonds.