Modulating stereoselectivity in allylic C(sp3)-H bond arylations via nickel and photoredox catalysis

Long Huang (), Marcin Szewczyk, Rajesh Kancherla, Bholanath Maity, Chen Zhu, Luigi Cavallo () and Magnus Rueping ()
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Long Huang: RWTH Aachen University
Marcin Szewczyk: RWTH Aachen University
Rajesh Kancherla: King Abdullah University of Science and Technology (KAUST)
Bholanath Maity: King Abdullah University of Science and Technology (KAUST)
Chen Zhu: King Abdullah University of Science and Technology (KAUST)
Luigi Cavallo: King Abdullah University of Science and Technology (KAUST)
Magnus Rueping: King Abdullah University of Science and Technology (KAUST)

Nature Communications, 2023, vol. 14, issue 1, 1-10

Abstract: Abstract While significant progress has been made in developing selective C-H bond cross-couplings in the field of radical chemistry, the site and stereoselectivity remain a long-standing challenge. Here, we present the successful development of stereodivergent allylic C(sp3)-H bond arylations through a systematic investigation of the direction and degree of stereoselectivity in the cross-coupling process. In contrast to the signature photosensitized geometrical isomerization of alkenes, the catalytic reaction demonstrates the feasibility of switching the C-C double bond stereoselectivity by means of ligand control as well as steric and electronic effects. Computational studies explain the stereochemical outcome and indicate that excitation of a Ni-allyl complex from singlet to a triplet state results in a spontaneous change of the allyl group coordination and that the subsequent isomerization can be directed by the choice of the ligand to achieve E/Z selectivity.

Date: 2023
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DOI: 10.1038/s41467-023-36103-0

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