Electrochemical Desaturative β‐Acylation of Cyclic N‐Aryl Amines

Radical Capture at Ni(II) Complexes: C-C, C-N, and C-O Bond Formation

10.26434/chemrxiv.8115860.v1 ◽

2019 ◽

Author(s):

Abolghasem (Gus) Bakhoda ◽

Stefan Wiese ◽

Christine Greene ◽

Bryan C. Figula ◽

Jeffery A. Bertke ◽

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Keyword(s):

Functional Groups ◽

Bond Formation ◽

Dft Studies ◽

Bond Forming ◽

Aryl Amines ◽

Shed Light ◽

Competing Pathways

The dinuclear b-diketiminato NiIItert-butoxide {[Me3NN]Ni}2(μ-OtBu)2 (2), synthesized from [Me3NN]Ni(2,4-lutidine) (1) and di-tert-butylperoxide, is a versatile precursor for the synthesis of a series of NiIIcomplexes [Me3NN]Ni-FG to illustrate C-C, C-N, and C-O bond formation at NiII via radicals. {[Me3NN]Ni}2(μ-OtBu)2 reacts with nitromethane, alkyl and aryl amines, acetophenone, benzamide, ammonia and phenols to deliver corresponding mono- or dinuclear [Me3NN]Ni-FG species (FG = O2NCH2, R-NH, ArNH, PhC(O)NH, PhC(O)CH2, NH2and OAr). Many of these NiII complexes are capable of capturing the benzylic radical PhCH(•)CH3 to deliver corresponding PhCH(FG)CH3 products featuring C-C, C-N or C-O bonds. DFT studies shed light on the mechanism of these transformations and suggest two competing pathways that depend on the nature of the functional groups. These radical capture reactions at [NiII]-FG complexes outline key C-C, C-N, and C-O bond forming steps and suggest new families of nickel radical relay catalysts.

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Faculty Opinions recommendation of Strategies to mitigate the bioactivation of aryl amines.

Faculty Opinions – Post-Publication Peer Review of the Biomedical Literature ◽

10.3410/f.738108714.793579623 ◽

2020 ◽

Author(s):

John Lowe

Keyword(s):

Aryl Amines

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Copper(ii) triflate catalyzed three-component reaction for the synthesis of 2,3-diarylquinoline derivatives using aryl amines, aryl aldehydes and styrene oxides

Organic & Biomolecular Chemistry ◽

10.1039/d1ob00125f ◽

2021 ◽

Vol 19 (14) ◽

pp. 3255-3262

Author(s):

Saghir Ali ◽

Abu T. Khan

Keyword(s):

Aryl Aldehydes ◽

Three Component Reaction ◽

Aryl Amines

An efficient and expedient synthetic protocol is reported for the synthesis of 2,3-diarylquinoline derivatives from readily available aryl amines, aryl aldehydes and styrene oxides using 10 mol% copper(ii) triflate by employing three-component reaction.

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