Copper‐Catalyzed Heteroarylsilylation of Unactivated Olefins through Distal Heteroaryl Migration

Zhang, Hong; Wu, Xinxin; Zhao, Qian; Zhu, Chen

doi:10.1002/asia.201800150

Cited by 50 publications

(6 citation statements)

References 63 publications

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“…Aryl alkynoates are reliable coupling partners in atom transfer radical cascade reactions, and various molecular frameworks have been constructed taking advantage of the radical acceptor property of the activated alkyne functionality. − Recently, this radical cascade has been advanced for 1,4-aryl migration that resembles Smiles rearrangement (see Scheme a). , All of these radical-based rearrangements were primarily performed at elevated temperature, and only trisubstituted olefins were obtained after the decarboxylation process (Path I, Scheme a) . We envisioned that the decarboxylation step would be interrupted if the radical-based Smiles rearrangement process can be executed under mild conditions.…”

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confidence: 56%

Radical Cascade Reaction of Aryl Alkynoates at Room Temperature: Synthesis of Fully Substituted α,β-Unsaturated Acids with Chalcogen Functionality

2018

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A radical-based cascade reaction has been devised for oxidative difunctionalization of aryl alkynoates at room temperature to access stereodefined fully substituted α,β-unsaturated acids bearing a chalcogen functionality in high yields (up to 95%). The protocol is operationally simple, metal-free, scalable, and suppresses the usual CO exclusion phenomenon. The utility of this method was showcased in the synthesis of vinyl halides, vinyl selenides, and 3,3-disubstituted indanones.

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confidence: 56%

Radical Cascade Reaction of Aryl Alkynoates at Room Temperature: Synthesis of Fully Substituted α,β-Unsaturated Acids with Chalcogen Functionality

2018

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“…The difluoroalkyl radical ( 21) is initially docked to the alkene, delivering a transient alkyl radical (22), which is subsequently trapped by the heteroaryl group forming a 5-membered ring intermediate (23). Then, the force of SO2 release promotes heteroaryl migration and gives a new difluoroalkyl radical (24), which after a further iodination step delivers the final product (25). The feasibility of this unprecedented protocol was demonstrated by difluoromethylheteroarylation of alkenes.…”

Section: Sulfone-based Bifunctional Reagents For Difunctionalization ...mentioning

confidence: 99%

Radical Heteroarylation of Alkenes and Alkanes via Heteroaryl Migration

Wei

Zhu

2022

Synlett

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Heteroarenes are important units in organic chemistry and are ubiquitous in natural products, pharmaceuticals, and numerous artificial molecules. Despite great efforts devoted to accessing heteroarenes, the development of new methods to efficiently produce heteroarenes remains a long-term interest. Recently, the strategy of radical-mediated heteroaryl migration has supplied a robust toolkit for the synthesis of a diversity of heteroaryl-containing compounds. This Account summarizes our recent achievements in this field and provides insight into the incorporation of heteroarenes into organic skeletons.

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“…The protocol was extensively applied to the concomitant construction of C–N, C–C, C–P, C–S, , and C–Si bonds along with the heteroaryl migration, leading to a portfolio of heteroarylfunctionalizations of unactivated alkenes by using various radical precursors (Scheme ).…”

Section: Difunctionalization Of Unactivated Alkenes Via Fgmmentioning

confidence: 99%

Radical-Mediated Remote Functional Group Migration

Zhu

2020

Acc. Chem. Res.

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268

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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 system (e.g., aryl, carbonyl, and heteroatom) is requisite to stabilize the nascent alkyl radical intermediate via p−π conjugation or p orbitals of the heteroatom. In contrast, the transformation of unactivated alkenes, such as aliphatic alkenes, remains challenging.To overcome this obstacle, we have recently disclosed the strategy of intramolecular distal functional group migration (FGM), which has been efficiently applied in radical difunctionalization of unactivated alkenes. A portfolio of functional groups, such as cyano, heteroaryl, oximino, formyl, and alkynyl groups, showcase the excellent migratory aptitude. Mechanistically, after the addition of an extrinsic radical to the alkene, the newly formed active alkyl radical is rapidly captured by the intramolecular migratory group to generate a cyclic intermediate. Subsequent cleavage of the cyclic C−C bond of the intermediate leads to the functionalized product through the FGM process. Based on the strategy of FGM, a set of elusive difunctionalizations of unactivated alkenes have been accomplished (Part A). Alongside this research, an upgraded highly efficient synthetic strategy, "dock-migration," is created for intermolecular difunctionalization of alkenes. A diversity of sulfone-based dual-function reagents are developed. The intermolecular transformation is initiated by docking the dual-function reagent to the alkene, followed by intramolecular migration of the functional group.Compared to the original FGM protocol, the scope of alkenes is significantly extended from the strategically placed tertiary alcoholsubstituted alkenes to general alkenes. Both activated and unactivated alkenes are well tolerated. By this approach, radical-mediated fluoroalkylheteroarylation, fluoroalkylalkynylation, and alkylation of alkenes have been achieved (Part B). Direct elaboration of C−H bonds into the targeted functional groups represents one of the most ideal and straightforward methods for molecular functionalization. The FGM strategy proves to be an ingenious tool for radical-mediated functionalization of remote unactivated C(sp 3 )−H bonds. Based on the FGM process, we have accomplished: (a) remote C(sp 3 )−H heteroarylation and cyanation of unprotected alcohols via the cascade of alkoxy radical-enabled hydrogen atom transfer (HAT) and intramolecular functional group (e.g., heteroaryl, cyano) migration, and (b) distal C(sp 3 )−H vinylation of propargylic alcohols through consecutive alkenyl radical-promoted HAT process and subsequent alkenyl migration (Part C).

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Copper‐Catalyzed Heteroarylsilylation of Unactivated Olefins through Distal Heteroaryl Migration

Cited by 50 publications

References 63 publications

Radical Cascade Reaction of Aryl Alkynoates at Room Temperature: Synthesis of Fully Substituted α,β-Unsaturated Acids with Chalcogen Functionality

Radical Cascade Reaction of Aryl Alkynoates at Room Temperature: Synthesis of Fully Substituted α,β-Unsaturated Acids with Chalcogen Functionality

Radical Heteroarylation of Alkenes and Alkanes via Heteroaryl Migration

Radical-Mediated Remote Functional Group Migration

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Copper‐Catalyzed Heteroarylsilylation of Unactivated Olefins through Distal Heteroaryl Migration

Cited by 50 publications

References 63 publications

Radical Cascade Reaction of Aryl Alkynoates at Room Temperature: Synthesis of Fully Substituted α,β-Unsaturated Acids with Chalcogen Functionality

Radical Cascade Reaction of Aryl Alkynoates at Room Temperature: Synthesis of Fully Substituted α,β-Unsaturated Acids with Chalcogen Functionality

Radical Heteroarylation of Alkenes and Alkanes via Heteroaryl ­Migration

Radical-Mediated Remote Functional Group Migration

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Radical Heteroarylation of Alkenes and Alkanes via Heteroaryl Migration