2020
DOI: 10.1021/acs.accounts.0c00306
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Radical-Mediated Remote Functional Group Migration

Abstract: Metrics & MoreArticle Recommendations CONSPECTUS: Alkenes are ubiquitous in natural products and are extensively used as synthetic feedstocks in multiple fields including organic synthesis, medicinal chemistry, and materials science. Radical-mediated difunctionalization of alkenes provides a powerful tactic for alkene utilization. Despite the considerable progress made in the past several decades, state-of-the-art methods are highly dependent upon activated alkenes in which a proximal group with a π-electron s… Show more

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Cited by 268 publications
(99 citation statements)
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“…Based on the experimental results and our knowledge in radical‐mediated heteroaryl migration, [19a] a plausible mechanism is outlined in Scheme 6. Single electron transfer (SET) between Cu I and the C‐Br bond of 1 generates the intermediate a , and initiates the transformation.…”
Section: Resultsmentioning
confidence: 99%
“…Based on the experimental results and our knowledge in radical‐mediated heteroaryl migration, [19a] a plausible mechanism is outlined in Scheme 6. Single electron transfer (SET) between Cu I and the C‐Br bond of 1 generates the intermediate a , and initiates the transformation.…”
Section: Resultsmentioning
confidence: 99%
“…[1][2][3][4][5][6][7] Most of the current approaches rely highly on the properties of alkenes; activated alkenes are usually suitable substrates, for example, styrenes, enol ethers, enamines, acrylates, and so forth, owing to the presence of p-π conjugation that stabilizes nascent alkyl radicals arising from radical addition to alkenes. To surmount the obstacles in radical difunctionalization of unactivated alkenes, the strategy of remote functional group migration (FGM) was unveiled, [8][9][10][11][12] and has been applied successfully to a set of elusive alkene transformations, including cyanation, 13,14 (hetero)arylation, [15][16][17][18][19] alkynylation, 20,21 alkenylation, [22][23][24][25][26] acylation, 27,28 and oximination. [28][29][30] Incorporation of a fluoroalkyl group (CF 3 , CF 2 R, or CFRR') to bioactive molecules usually rendered a substantial change in lipophilicity, metabolic stability, and other bioactivities.…”
Section: Introductionmentioning
confidence: 99%
“…In addition to the success of radical polymerization for making synthetic polymers, organic radical reactions have also become an increasing important tools for preparation of small molecules through radical addition, cyclization, cascade bond formation, H-atom and group-transfer, and radical-radical coupling reactions [1,2]. Active researches on direct C-H bond functionalization [3], remote (distal) functionalization [4], Smile-type ipso-group rearrangement [5], cascade reaction [6], photoredox catalysis [7], and electrochemical reaction [8] have significantly fueled the chemistry of synthetic radicals.…”
Section: Introductionmentioning
confidence: 99%
“…Presented in this article are one-pot radical addition, oxidation and nucleophilic addition reactions to incorporate two functional groups to alkenes or alkynes. The difunctionalization could be accomplished through direct 1,2-addition (Scheme 1I-A), 1,2-functionalization involving Smiles-type ispo aryl group migration (Scheme 1I-B) [4,5], or 1,n-functionalization involving H-atom transfer (Scheme 1I-C) [4][5][6]. The majority examples in this paper are direct 1,2-additions.…”
Section: Introductionmentioning
confidence: 99%