RT Journal Article
T1 Catalytic Lewis Base Additive Enables Selective Copper-Catalyzed Borylative α-C–H Allylation of Alicyclic Amines
A1 Pérez Saavedra, Borja
A1 Velasco Rubio, Álvaro
A1 Rivera Chao, Eva
A1 Varela Carrete, Jesús Ángel
A1 Saá Rodríguez, Carlos
A1 Fañanás-Mastral, Martín
K1 Allenes
K1 Chemical reactions
K1 Lewis bases
K1 Ligands
AB Functionalized 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.
PB ACS Publications
SN 0002-7863
YR 2022
FD 2022
LK http://hdl.handle.net/10347/29186
UL http://hdl.handle.net/10347/29186
LA eng
NO J. Am. Chem. Soc. (2022). https://doi.org/10.1021/jacs.2c07969
NO Financial support from the Spanish Ministry of Science and Innovation (PID2020-118237RB-I00, PID2020-118048GB-I00, and the ORFEO-CINQA network RED2018-102387-T), Xunta de Galicia (ED431C 2018/04; Centro singular de investigación de Galicia accreditation 2019-2022, ED431G 2019/03), and the European Union (European Regional Development Fund, ERDF) is gratefully acknowledged. B.P.-S., A.V.-R., and E.R.-C. thank Xunta de Galicia for predoctoral fellowships. We also acknowledge the use of RIAIDT-USC analytical facilities and CESGA (Xunta de Galicia) for computational time
DS Minerva
RD 28 abr 2026