Radical‐Promoted C−C Bond Cleavage: A Deconstructive Approach for Selective Functionalization

Abstract

Just as “Deconstructivism” appeared as a novel movement in architecture in the 1980s, deconstructive approaches have recently emerged as excellent strategies for scaffold hopping modifications in chemistry. The deconstruction and functionalization of cyclic molecules mainly involves the cleavage of the carbon–carbon (C−C) bond followed by the construction of new bonds. The cleavage of inert C−C single bonds, especially in unstrained cycles, and their subsequent functionalization is still one of the most sought‐after challenges in chemistry. In this vein, radical‐mediated strategies provide an excellent approach for achieving this aim. This minireview is an outline of the history of homolytic cleavage and highlights the recent advances in exploring new chemical space by deconstructive functionalization.

Catalytic carbon-carbon bond cleavage and carbon-element bond formation give new life for polyolefins as biodegradable surfactants

“…Current methods that install a metal center by breaking a carbon-carbon bond, however, are limited to positions activated either by thermodynamically weakened bonds or directing functional groups (Figure 1A). [4][5][6][7] On the other hand, established C-C bond cleavages involving only sp 3 -hybridized carbon centers generally do not provide new carbon-heteroatom bonds. For example, alkane metathesis (Figure 1B) alters chain lengths without introducing new functional groups.…”

Generation of Alkyl Radicals: From the Tyranny of Tin to the Photon Democracy

“… 76 − 81 As an alternative, the photochemical radical generation may induce a ring-opening in strained structures like cyclobutanes, to form a substituted alkyl radical ( Figure 2 F). 82 …”

Oxidative Fluorination of Cyclopropylamides through Organic Photoredox Catalysis

“…[1] Among these methods, the formation of C(sp 3 ) À F bonds through ring opening fluorination of carbocycles is an attractive route. [2] While success has been achieved in ringopening fluorination of arylcyclopropanes (Scheme 1 A), [3] cyclopropanols, [4] and cyclobutanols [4a,b] (Scheme 1 B), their nitrogen-substituted counterparts were not studied yet, despite the importance of nitrogen-containing fluorinated drugs and agrochemicals.…”