向重氮甲烷-硼烷加合物的单电子转移引发C-H键活化。
Single Electron Transfer to Diazomethane-Borane Adducts Prompts C-H Bond Activations.
作者信息
Cao Levy L, Zhou Jiliang, Qu Zheng-Wang, Stephan Douglas W
机构信息
Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario, M5S3H6, Canada.
Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Beringstrasse 4, 53115, Bonn, Germany.
出版信息
Angew Chem Int Ed Engl. 2019 Dec 16;58(51):18487-18491. doi: 10.1002/anie.201912338. Epub 2019 Oct 30.
While (Ph CN )B(C F ) is unstable, single electron transfer from Cp* Co affords the isolation of stable products [Cp* Co][Ph CNNHB(C F ) ] 1 and [CpCo(C Me CH B(C F ) )] 2. The analogous combination of Ph CN and BPh showed no evidence of adduct formation and yet single electron transfer from Cp Cr affords the species [Cp* Cr][PhC(C H )NNBPh ] 3 and [Cp* Cr][Ph CNNHBPh ] 4. Computations showed both reactions proceed via transient radical anions of the diphenyldiazomethane-borane adducts to effect C-H bond activations.
虽然(PhCN)B(CF)不稳定，但来自CpCo的单电子转移使得能够分离出稳定产物[CpCo][PhCNNHB(CF)]1和[CpCo(CMeCHB(CF))]2。PhCN和BPh的类似组合没有形成加合物的迹象，但来自CpCr的单电子转移产生了物种[CpCr][PhC(CH)NNBPh]3和[CpCr][PhCNNHBPh]4。计算表明，这两个反应都是通过二苯基重氮甲烷-硼烷加合物的瞬态自由基阴离子进行的，以实现C-H键活化。
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