biostudies-literatureBruckner TEuropean Research CouncilDeutsche ForschungsgemeinschaftAlexander von Humboldt-StiftungCoordenação de Aperfeiçoamento de Pessoal de Nível Superiore202213284https://www.ebi.ac.uk/biostudies/studies/S-EPMC10107673biostudies-literatureUnknown62(5)Carbene-stabilized diborynes of the form LBBL (L=N-heterocyclic carbene (NHC) or cyclic alkyl(amino)carbene (CAAC)) induce rapid, high yielding, intermolecular ortho-C-H borylation at N-heterocycles at room temperature. A simple pyridyldiborene is formed when an NHC-stabilized diboryne is combined with pyridine, while a CAAC-stabilized diboryne leads to activation of two pyridine molecules to give a tricyclic alkylideneborane, which can be forced to undergo a further H-shift resulting in a zwitterionic, doubly benzo-fused 1,3,2,5-diazadiborinine by heating. Use of the extended N-heteroaromatic quinoline leads to a borylmethyleneborane under mild conditions via an unprecedented boron-carbon exchange process.Angewandte Chemie (International ed. in English)Metal-Free Intermolecular C-H Borylation of N-Heterocycles at B-B Multiple Bonds.PMC10107673466754611669054Ritschel BDuwe DBraunschweig HFantuzzi FDietz MMarkl CDewhurst RDBruckner TJimenez-Halla JOCfalseMetal-Free Intermolecular C-H Borylation of N-Heterocycles at B-B Multiple Bonds.Carbene-stabilized diborynes of the form LBBL (L=N-heterocyclic carbene (NHC) or cyclic alkyl(amino)carbene (CAAC)) induce rapid, high yielding, intermolecular ortho-C-H borylation at N-heterocycles at room temperature. A simple pyridyldiborene is formed when an NHC-stabilized diboryne is combined with pyridine, while a CAAC-stabilized diboryne leads to activation of two pyridine molecules to give a tricyclic alkylideneborane, which can be forced to undergo a further H-shift resulting in a zwitterionic, doubly benzo-fused 1,3,2,5-diazadiborinine by heating. Use of the extended N-heteroaromatic quinoline leads to a borylmethyleneborane under mild conditions via an unprecedented boron-carbon exchange process.2023-01-01T00:00:00Z2023 Jan2025-04-26T05:00:05.347Z2025-04-06T11:23:28.393ZS-EPMC101076733644065910.1002/anie.202213284