AIBN as an Electrophilic Reagent for Cyano Group Transfer
AIBN as an Electrophilic Reagent for Cyano Group Transfer
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DOI：
10.1021/acs.joc.2c02859
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发表时间：
2023-02-08
影响因子：
3.6
通讯作者：
Alabugin，Igor V.
中科院分区：
文献类型：
--
作者：
Elliott，Quintin;Alabugin，Igor V.
AIBN是一种简便的亲电氰化试剂，可在温和的条件下将ArLi转化为ArCN。加成/碎裂级联反应受Li···N络合作用的控制，其中AIBN氮基协助几乎无障碍地碎裂成所需的ArCN产物。碎裂副产物中的酸性C-H键通过质子化部分消耗ArLi。密度泛函理论计算和同位素标记探讨了该反应的机理，并解释了在与BuLi的反应中转换为取代肼的原因。
AIBN is a convenient electrophilic cyanation reagent for transforming ArLi into ArCN under mild conditions. The addition/fragmentation cascade is controlled by Li···N chelation in which AIBN nitrogens assist in the nearly barrierless fragmentation into the desired ArCN product. Acidic C–H bonds in the fragmented byproduct partially consume ArLi by protonation. Density functional theory calculations and isotopic labeling probe the mechanism and explain the switch to substituted hydrazones in reactions with BuLi.