Vignolle Joan, Asay Matthew, Miqueu Karinne, Bourissou Didier, Bertrand Guy
Laboratoire Hétérochimie Fondamentale et Appliquée du CNRS (UMR 5069), Université Paul Sabatier, 118, route de Narbonne, 31062 Toulouse Cedex 09, France.
Org Lett. 2008 Oct 2;10(19):4299-302. doi: 10.1021/ol801670z. Epub 2008 Sep 3.
The biphenyl and binaphthyl diisopropylaminocarbenes were found to be only transient species that spontaneously and quantitatively rearrange into the corresponding aminofluorenes. DFT calculations confirm that these insertion reactions of aminocarbenes into proximal aromatic C-H bonds require only a moderate energy barrier and support a concerted, strongly asynchronous, mechanism dominated by C arom-->C carbene proton transfer.
联苯和联萘二异丙基氨基卡宾被发现只是瞬态物种,它们会自发且定量地重排成相应的氨基芴。密度泛函理论计算证实,这些氨基卡宾插入近端芳族C-H键的反应仅需要适度的能垒,并支持一种由C芳基→C卡宾质子转移主导的协同、强异步机制。