Substrate-Rhodium Cooperativity in Photoinduced ortho-Alkynylation of Arenes.

Autor: Saha A; Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India., Ghosh A; Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India., Guin S; Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India., Panda S; Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India., Mal DK; Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India., Majumdar A; Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India., Akita M; Tokyo Tech World Research Hub Initiative (WRHI), Laboratory for Chemistry and Life Science, Tokyo Institute of Technology, Tokyo, Japan., Maiti D; Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2022 Oct 17; Vol. 61 (42), pp. e202210492. Date of Electronic Publication: 2022 Sep 12.
DOI: 10.1002/anie.202210492
Abstrakt: In the realm of metallaphotocatalytic C-H activation strategy, the direct excitation of the transition metal which plays the dual role of light energy harnessing alongside performing the bond breaking and forming is a rare phenomenon. In this context we have developed the first photo-induced Rh-catalyzed ortho-alkynylation under ambient conditions without the requirement of silver salt, photocatalyst (PC) or any engineered substrate or catalyst. The transformation functions by the specific cooperative effect of a six-membered rhodacycle which is the photo-responsive species. The catalytic system allows the conjugation of arenes with sp 3 -rich pharmacophoric fragments. The control experiments as well as the computational studies resolve the mechanistic intricacies for this transformation. An outer sphere electron transfer process from Rh to alkynyl radical is operative for the present photo-induced transformation over the more common oxidative addition or 1,2-migratory insertion pathways.
(© 2022 Wiley-VCH GmbH.)
Databáze: MEDLINE
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