98%
921
2 minutes
20
Decyanation after α-functionalization by exploiting the inherent properties of cyano groups enables the strategic assembly of a carbon scaffold. Herein, we demonstrate an amine-ligated boryl radical-mediated cyano group transfer (CGT) strategy of malononitriles under photocatalytic conditions. This strategy allows for the cleavage of C(sp)-CN and the formation of C(sp)-D and C(sp) to realize decyanative deuteration and cyclization via radical-polar crossover. Computational studies successfully demonstrated the reactivity of CGT promoters can be accurately assessed.
Download full-text PDF |
Source |
---|---|
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11934141 | PMC |
http://dx.doi.org/10.1021/acs.orglett.4c04701 | DOI Listing |
Org Lett
July 2025
Department of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan.
Herein, we describe a photocatalytic strategy for decyanative hydrofunctionalization of styrenes with α-heteroatom-substituted acetonitriles. This strategy facilitates the generation of α-heteroatom methyl radicals from acetonitriles through cyano group transfer (CGT) enabled by amine-ligated boryl radicals. The broad applicability of this method is demonstrated by its successful application in late-stage functionalization of bioactive compounds.
View Article and Find Full Text PDFOrg Lett
March 2025
Department of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan.
Decyanation after α-functionalization by exploiting the inherent properties of cyano groups enables the strategic assembly of a carbon scaffold. Herein, we demonstrate an amine-ligated boryl radical-mediated cyano group transfer (CGT) strategy of malononitriles under photocatalytic conditions. This strategy allows for the cleavage of C(sp)-CN and the formation of C(sp)-D and C(sp) to realize decyanative deuteration and cyclization via radical-polar crossover.
View Article and Find Full Text PDFChem Sci
October 2024
Institute of Organic Chemistry, RWTH Aachen University Landoltweg 1 Aachen 52056 Germany
Alkynes are a crucial class of materials with application across the wide range of chemical disciplines. The alkynylation of alkyl halides presents an ideal strategy for assembling these materials. Current methods rely on the intrinsic electrophilic nature of alkyl halides to couple with nucleophilic acetylenic systems, but these methods faces limitations in terms of applicability and generality.
View Article and Find Full Text PDFJ Org Chem
September 2024
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China.
Nickel/photoredox catalysis has emerged as a powerful platform for exploring nontraditional and challenging cross-couplings. Herein, a metallaphotoredox catalytic protocol has been developed on the basis of a tertiary amine-ligated boryl radical-induced halogen atom transfer process under blue-light irradiation. A wide variety of aryl and heteroaryl bromides featuring different functional groups and pharmaceutical moieties were facilely coupled to rapidly install C(sp)-enriched aromatic scaffolds.
View Article and Find Full Text PDFJ Am Chem Soc
August 2024
Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52056 Aachen, Germany.
Alkyl organoborons are powerful materials for the construction of C()-C() bonds, predominantly via Suzuki-Miyaura cross-coupling. These species are generally assembled using 2-electron processes that harness the ability of boron reagents to act as both electrophiles and nucleophiles. Herein, we demonstrate an alternative borylation strategy based on the reactivity of amine-ligated boryl radicals.
View Article and Find Full Text PDF