A general N-alkylation platform via copper metallaphotoredox and silyl radical activation of alkyl halides

The first iron-catalyzed three-component cross-coupling of unactivated olefins with alkyl halides and Grignard reagents is reported. The reaction operates under fast turnover frequency and tolerates a diverse range of sp2-hybridized nucleophiles, alkyl halides, and unactivated olefins bearing diverse functional groups to yield the desired 1,2-alkylarylated products with high regiocontrol. Further, we demonstrate that this protocol is amenable for the synthesis of new (hetero)carbocycles including tetrahydrofurans and pyrrolidines via a three-component radical cascade cyclization/arylation that forges three new C-C bonds.

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Design and Development of Fe-Catalyzed Intra- and Intermolecular Carbofunctionalization of Vinyl Cyclopropanes

10.26434/chemrxiv.9858500.v1 ◽

2019 ◽

Cited By ~ 1

Author(s):

Lei Liu ◽

Wes Lee ◽

Mingbin Yuan ◽

Chris Acha ◽

Michael B. Geherty ◽

...

Keyword(s):

Bond Formation ◽

Cross Coupling ◽

Alkyl Halides ◽

Grignard Reagents ◽

Mechanistic Studies ◽

Radical Intermediates ◽

Design And Implementation ◽

Solvent Cage ◽

Radical Cascade ◽

Radical Processes

Design and implementation of the first (asymmetric) Fe-catalyzed intra- and intermolecular difunctionalization of vinyl cyclopropanes (VCPs) with alkyl halides and aryl Grignard reagents has been realized via a mechanistically driven approach. Mechanistic studies support the diffusion of the alkyl radical intermediates out of the solvent cage to participate in an intra- or -intermolecular radical cascade with the VCP followed by re-entering the Fe radical cross-coupling cycle to undergo selective C(sp2)-C(sp3) bond formation. Overall, we provide new design principles for Fe-mediated radical processes and underscore the potential of using combined computations and experiments to accelerate the development of challenging transformations.

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Nickel and Cobalt-Catalyzed Coupling of Alkyl Halides with Alkenes via Heck Reactions and Radical Conjugate Addition

Mini-Reviews in Medicinal Chemistry ◽

10.2174/1389557511313060003 ◽

2013 ◽

Vol 13 (6) ◽

pp. 802-813 ◽

Cited By ~ 17

Author(s):

Qun Qian ◽

Zhenhua Zang ◽

Yang Chen ◽

Weiqi Tong ◽

Hegui Gong

Keyword(s):

Conjugate Addition ◽

Alkyl Halides ◽

Heck Reactions

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Nickel-Catalyzed Multicomponent Coupling Reaction of Alkyl Halides, Isocyanides and H2O: An Expedient Way to Access Alkyl Amides

Synthesis ◽

10.1055/s-0040-1707229 ◽

2020 ◽

Vol 52 (22) ◽

pp. 3466-3472

Author(s):

Yunkui Liu ◽

Bingwei Zhou ◽

Qiao Li ◽

Hongwei Jin

Keyword(s):

Functional Group ◽

Coupling Reaction ◽

Alkyl Halides ◽

Previous Literature ◽

Catalytic Cycle ◽

Reaction Conditions ◽

Multicomponent Coupling ◽

Easy Operation

We herein describe a Ni-catalyzed multicomponent coupling reaction of alkyl halides, isocyanides, and H2O to access alkyl amides. Bench-stable NiCl2(dppp) is competent to initiate this transformation under mild reaction conditions, thus allowing easy operation and adding practical value. Substrate scope studies revealed a broad functional group tolerance and generality of primary and secondary alkyl halides in this protocol. A plausible catalytic cycle via a SET process is proposed based on preliminary experiments and previous literature.

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