SUPERELECTROPHILES
SUPERELECTROPHILES
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DOI：
10.1002/anie.199307673
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发表时间：
1993-06-01
期刊：
影响因子：
--
通讯作者：
OLAH, GA
中科院分区：
文献类型：
--
作者：
OLAH, GA
亲电试剂能够与强布朗斯特酸或路易斯酸进一步相互作用（配位、溶剂化），可以通过这种方式活化。与常规条件下的亲本化合物相比，它们的反应活性得到了极大的增强，这表明形成了超亲电试剂（即，具有双重缺电（dipositive）性质的亲电试剂，其反应活性大大超过亲本亲电试剂）。作为代表性的例子，讨论了以下亲电试剂在超酸性和相关的强亲电介质中的原解或亲电活化：氧鎓、碳鎓、磺酸、硒鎓和碲鎓离子；酰基阳离子;质子化的CO， CO2， COS，以及碳和硫碳酸；杂原子取代碳正离子（以及它们的一些硼类似物）；halonium离子;氮（包括氮）和咔氮离子。重点放在实验化学研究和理论处理所涉及的系统。原水合氢离子（双质子化水）及其类似物原磺化氢离子（原磺化氢离子）作为质子活化离子的原型具有特殊的意义。以超亲电试剂为例，讨论了原乙酰基和原甲酰基反应（二质子化一氧化碳）、二质子化碳酸和二氧化碳、二质子化氰化氢和腈以及原硝基反应等及其新出现的化学反应。
Electrophiles that are capable of further interaction (coordination, solvation) with strong Bronsted or Lewis acids can be activated in this way. The resulting enhancement of their reactivity is great compared to that of their parent compounds under conventional conditions and indicates superelectrophile formation (i.e., electrophiles with doubly electrodeficient (dipositive) nature whose reactivity substantially exceeds that of their parent electrophiles). As representative examples the protolytic or electrophilic activation of the following electrophiles in superacidic and related strongly electrophilic media is discussed: oxonium, carboxonium, sulfonium, selenonium, and telluronium ions; acyl cations; protonated CO, CO2, COS, and carbonic and thiocarbonic acids; heteroatom-substituted carbocations (and some of their boron analogs); halonium ions; azonium (including nitronium) and carbazonium ions. Emphasis is placed on both experimental chemical investigations and theoretical treatment of the involved systems. As prototypes for protolytically activated onium ions, the protohydronium dication (diprotonated water) and its sulfur analogue, the protosulfonium dication, are of particular significance. The protoacetyl and protoformyl dication (diprotonated carbon monoxide), diprotonated carbonic acid and carbon dioxide, diprotonated hydrogen cyanide and nitriles, as well as the protonitronium dication -among others and their emerging chemistry are discussed as examples of superelectrophiles.