Photoinduced Remote Functionalisations by Iminyl Radical Promoted C−C and C−H Bond Cleavage Cascades
نویسندگان
چکیده
A photoinduced cascade strategy leading to a variety of differentially functionalised nitriles and ketones has been developed. These reactions rely on the oxidative generation of iminyl radicals from simple oximes. Radical transposition by C(sp3 )-(sp3 ) and C(sp3 )-H bond cleavage gives access to distal carbon radicals that undergo SH 2 functionalisations. These mild, visible-light-mediated procedures can be used for remote fluorination, chlorination, and azidation, and were applied to the modification of bioactive and structurally complex molecules.
منابع مشابه
H2 Elimination and C-C Bond Cleavage of Propene: A Theoretical Research
Propene dissociation channels were characterized by ab initio CCSD(T)/6-311++g(d,p) calculations. Inthis work the detailed mechanism of propene dissociation to C2H4+CH2, C2H2+H+CH3, C2H2+CH4 andC3H3+H2+H have been investigated. According to our calculations, ten fragments can be classified intofive dissociated channels. Our results point out that two mechanisms come into play in the H2 eliminat...
متن کاملThe benzoyl peroxide-promoted functionalization of simple alkanes with 2-aryl phenyl isonitrile.
The benzoyl peroxide (BPO)-promoted phenanthridinylation of simple alkanes with isonitrile is developed via C(sp(3))-H and C(sp(2))-H bond cleavage. This procedure is featured by dual C-C bond formation proceeding with the addition of an alkyl radical to isonitrile followed by radical aromatic cyclization.
متن کاملA Facile and Environmental Friendly Method for C=N Bond Cleavage of Imines Using p-Toluenesulfonic Acid in Solid State
A simple, efficient and clean procedure has been developed for the cleavage of imines C=N bond. Deprotection of imines to their parent carbonyl and amine compounds was achieved using p-toluenesulfonic acid in the solid state condition at 25-45 ˚C. The salient features of this methodology are shorter reaction times, cheap processing, high yields of product and easy availability of the catalyst. ...
متن کاملAnomalous C-C bond cleavage in sulfur-centered cation radicals containing a vicinal hydroxy group.
1,3-dithianyl cation radicals having alpha-hydroxy-neopentyl or similar groups in position 2, which are generated via oxidative photoinduced electron transfer, undergo anomalous fragmentation necessitating refinement of the accepted mechanism. Experimental and computational data support a rationale in which proton abstraction from the hydroxy group in the initial cation radical does not cause a...
متن کاملA remote C–C bond cleavage–enabled skeletal reorganization: Access to medium-/large-sized cyclic alkenes
Although great success has been achieved in selective C-C bond cleavage via the intramolecular radical remote migration process of several carbon-based groups, the development of the radical-based remote vinyl migration process remains a formidable challenge because of the energetically unfavorable process. To address this problem, we report here, for the first time, a novel C-C bond reorganiza...
متن کامل