Intermolecular Redox‐Neutral Amine C−H Functionalization Induced by the Strong Boron Lewis Acid B(C6F5)3 in the Frustrated Lewis Pair Regime. Issue 19 (15th March 2017)

• Record Type: Journal Article
• Authors: Chen, Guo‐Qiang; Kehr, Gerald; Daniliuc, Constantin G.; Bursch, Markus; Grimme, Stefan; Erker, Gerhard
• Is Part Of: Chemistry. Volume 23:Issue 19(2017)
• Page Start: 4723
• Page End: 4729
• Publication Date: 2017-03-15
• Subjects: boron -- C−C coupling -- C−H activation -- hydride transfer -- nitrogen; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201700477
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: N, N ‐Dimethylmesitylamine undergoes an intermolecular redox‐neutral C−H activation/C−C coupling process upon treatment with dimethyl acetylenedicarboxylate and the strong boron Lewis acid B(C6 F5 )3 . Similarly, N, N ‐dimethylmesitylamine reacts with two molar equivalents of ethyl acrylate to give the respective unsaturated coupling product with H2 transfer to the acrylic ester to form the ethyl propionate/B(C6 F5 )3 adduct. N, N ‐Dimethylmesitylamine also undergoes a C−H activation at the benzylic ortho sp 3 ‐carbon atom with dihydrogen formation upon treatment with Piers' borane [HB(C6 F5 )2 ]. The last two reactions of N, N ‐dimethylmesitylamine were analyzed by DFT calculations. Abstract : Frustration leads to activation : Intermolecular C−C coupling of amines with α, β‐unsaturated carbonyl compounds under C−H activation is induced by B(C6 F5 )3 serving as hydride shuttle (see scheme).