Pérez Saavedra, BorjaVelasco Rubio, ÁlvaroRivera Chao, EvaVarela Carrete, Jesús ÁngelSaá Rodríguez, CarlosFañanás-Mastral, Martín2022-08-312022-08-312022J. Am. Chem. Soc. (2022). https://doi.org/10.1021/jacs.2c079690002-7863http://hdl.handle.net/10347/29186Functionalized alicyclic amines are important building blocks for the synthesis of bioactive natural compounds and drugs. Existing methods of functionalization are typically limited to the synthesis of protected amines or the use of highly basic organometallic reagents that can compromise functional group tolerance. Here, we report a novel approach that enables the transformation of O-benzoyl hydroxylamines into α-functionalized cyclic secondary amines by means of a copper-catalyzed regio-, stereo-, and chemoselective coupling with allenes and bis(pinacolato)diboron. A key feature of the present transformation is the use of a catalytic Lewis base additive which inhibits the competing C–N bond forming reaction between the catalytically generated boron-substituted allylcopper intermediate with the O-benzoyl hydroxylamine, thus enabling in situ transformation of the latter into an alicyclic imine which undergoes selective C–C bond formation with the allylcopper species.eng© 2022 The Authors. Published by ACS. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/)Atribución 4.0 Internacionalhttp://creativecommons.org/licenses/by/4.0/AllenesChemical reactionsLewis basesLigandsjournal article10.1021/jacs.2c079691520-5126open access