Chemoselective bond activation by unidirectional and asynchronous PCET using ketone photoredox catalysts.

Autor:	Sun R; Department of Chemistry and Chemical Biology, Harvard University 12 Oxford Street Cambridge MA 02138 USA dnocera@fas.harvard.edu., Ruccolo S; Department of Chemistry and Chemical Biology, Harvard University 12 Oxford Street Cambridge MA 02138 USA dnocera@fas.harvard.edu., Nascimento DL; Department of Chemistry and Chemical Biology, Harvard University 12 Oxford Street Cambridge MA 02138 USA dnocera@fas.harvard.edu., Qin Y; Department of Chemistry and Chemical Biology, Harvard University 12 Oxford Street Cambridge MA 02138 USA dnocera@fas.harvard.edu., Hibbert N; Department of Chemistry and Chemical Biology, Harvard University 12 Oxford Street Cambridge MA 02138 USA dnocera@fas.harvard.edu., Nocera DG; Department of Chemistry and Chemical Biology, Harvard University 12 Oxford Street Cambridge MA 02138 USA dnocera@fas.harvard.edu.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2023 Nov 02; Vol. 14 (47), pp. 13776-13782. Date of Electronic Publication: 2023 Nov 02 (Print Publication: 2023).
DOI:	10.1039/d3sc04362b
Abstrakt:	The triplet excited states of ketones are found to effect selective H-atom abstraction from strong amide N-H bonds in the presence of weaker C-H bonds through a proton-coupled electron transfer (PCET) pathway. This chemoselectivity, which results from differences in ionization energies (IEs) between functional groups rather than bond dissociation energies (BDEs) arises from the asynchronicity between electron and proton transfer in the PCET process. We show how this strategy may be leveraged to achieve the intramolecular anti-Markovnikov hydroamidation of alkenes to form lactams using camphorquinone as an inexpensive and sustainable photocatalyst. Competing Interests: There are no conflicts to declare. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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