Visible-Light-Promoted Site-Specific and Diverse Functionalization of a C(sp³)–C(sp³) Bond Adjacent to an Arene

Abstract

We report here a strategy for inert C−C bond functionalization. Site-specific cleavage and functionalization of a saturated C(sp 3 )−C(sp 3 ) bond via a visible-light-induced radical process have been achieved. The general features of this reaction are as follows. (1) Both linear and cyclic C(sp 3 )−C(sp 3 ) bonds with a vicinal arene can be specifically functionalized. (2) One carbon is converted into a ketone, and another can be tunably converted into nitrile, peroxide, or halide. (3) The typical conditions include 1.0 mol % of Ru(bpy) 3 Cl 2 , 1.0 or 5.0 equiv of Zhdankin reagent, white CFL (24 W), open flask, and room temperature. These reactions offer powerful tools to modify carbon skeletons that are intractable by conventional methods. Good selectivity and functional group tolerance, together with mild and open air conditions, make these transformations valuable and attractive.

Site-Specific Oxidation of (sp3)C–C(sp3)/H Bonds by NaNO2/HCl

“…Recently, a few elegant strategies for selective cleavage of specific (sp 3 )­C–C­(sp 3 ) bonds in amines, alcohols, and aryl alkanes have been achieved (Scheme a–c). Nevertheless, most of these systems suffer from excess chemical oxidants, limited substrate scope, or hash conditions.…”

Photo-mediated selective deconstructive geminal dihalogenation of trisubstituted alkenes

“…Light irradiation induces the homolysis of the labile I-O bond to generate the reactive oxygen radical species IV 43,45,46 . Carbon radical V is formed by β-scission of radical IV and subsequent iodination with the iodine radical or DIH accomplishes product VI 43,[46][47][48][49][50][51] .…”

Copper‐Catalyzed Aerobic Oxidative Cleavage of Unstrained Carbon‐Carbon Bonds of 1,1‐Disubstituted Alkenes with Sulfonyl Hydrazides

“…While our manuscript was under preparation, an example of the combination of hydrogen atom transfer (HAT) with alkoxyl radical, derived from alkyl radical capturing dioxygen, for the diverse functionalization of C—C bond adjacent to arene was reported by Liu's group (Scheme 1b). [ 7 ]…”