Ni-catalyzed reductive addition of alkyl halides to isocyanides

This work emphasizes Ni-catalyzed reductive trapping of secondary and tertiary alkyl radicals with both aryl isocyanides affording 6-alkylated phenanthridine in good yields. The employment of carbene ligands represents the examples of generation of alkyl radicals from the halide precursors under Ni-catalyzed reductive conditions.

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General Electrochemical Minisci Alkylation of N-Heteroarenes with Alkyl Halides

10.21203/rs.3.rs-1229384/v1 ◽

2022 ◽

Author(s):

Jose Aleman

Keyword(s):

Natural Products ◽

Functional Group ◽

Environmentally Friendly ◽

Building Blocks ◽

Alkyl Halides ◽

Alkyl Radicals ◽

First Time ◽

Very High ◽

Tertiary Alkyl

Abstract Herein, we report, for the first time, a general, facile and environmentally friendly Minisci-type alkylation of N-heteroarenes under simple and straightforward electrochemical conditions using widely available alkyl halides as radical precursors. Primary, secondary and tertiary alkyl radicals have shown to be efficiently generated and coupled with a large variety of N-heteroarenes. The method presents a very high functional group tolerance, including various heterocyclic-based natural products, which highlights the robustness of the methodology. This applicability has been further proved in the synthesis of various interesting biologically valuable building blocks. In addition, we have proposed a mechanism based on different proofs and electrochemical evidences.

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Amine synthesis via iron-catalysed reductive coupling of nitroarenes with alkyl halides

Nature Communications ◽

10.1038/ncomms12494 ◽

2016 ◽

Vol 7 (1) ◽

Cited By ~ 65

Author(s):

Chi Wai Cheung ◽

Xile Hu

Keyword(s):

Organic Molecules ◽

Functional Group ◽

Iron Catalyst ◽

Alkyl Halides ◽

Mechanistic Study ◽

Reductive Coupling ◽

Alkyl Radicals ◽

Aryl Amines ◽

Tertiary Alkyl ◽

General Method

Abstract (Hetero)Aryl amines, an important class of organic molecules in medicinal chemistry, are most commonly synthesized from anilines, which are in turn synthesized by hydrogenation of nitroarenes. Amine synthesis directly from nitroarenes is attractive due to improved step economy and functional group compatibility. Despite these potential advantages, there is yet no general method for the synthesis of (hetero)aryl amines by carbon–nitrogen cross-coupling of nitroarenes. Here we report the reductive coupling of nitroarenes with alkyl halides to yield (hetero)aryl amines. A simple iron catalyst enables the coupling with numerous primary, secondary and tertiary alkyl halides. Broad scope and high functional group tolerance are demonstrated. Mechanistic study suggests that nitrosoarenes and alkyl radicals are involved as intermediates. This new C–N coupling method provides general and step-economical access to aryl amines.

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ChemInform Abstract: ACTIVATION OF REDUCING AGENTS. SODIUM HYDRIDE-CONTAINING COMPLEX REDUCING AGENTS. 16. FECRACO, A NEW REAGENT FOR THE CARBONYLATION OF PRIMARY, SECONDARY, AND TERTIARY ALKYL HALIDES AT ATMOSPHERIC PRESSURE

Chemischer Informationsdienst ◽

10.1002/chin.198149138 ◽

1981 ◽

Vol 12 (49) ◽

Author(s):

J.-J. BRUNET ◽

C. SIDOT ◽

P. CAUBERE

Keyword(s):

Atmospheric Pressure ◽

Sodium Hydride ◽

Reducing Agents ◽

Alkyl Halides ◽

Tertiary Alkyl

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Tertiary alkyl halides as growth activator and inhibitor for novel atomic layer deposition of low resistive titanium nitride

AIP Advances ◽

10.1063/5.0031127 ◽

2021 ◽

Vol 11 (1) ◽

pp. 015218

Author(s):

Changbong Yeon ◽

Jaesun Jung ◽

Hyeran Byun ◽

Kok Chew Tan ◽

Taeho Song ◽

...

Keyword(s):

Atomic Layer Deposition ◽

Titanium Nitride ◽

Atomic Layer ◽

Alkyl Halides ◽

Layer Deposition ◽

Tertiary Alkyl

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Mizoroki–Heck type reactions and synthesis of 1,4-dicarbonyl compounds by heterogeneous organic semiconductor photocatalysis

Green Chemistry ◽

10.1039/d0gc03792c ◽

2021 ◽

Vol 23 (5) ◽

pp. 2017-2024

Author(s):

Jagadish Khamrai ◽

Saikat Das ◽

Aleksandr Savateev ◽

Markus Antonietti ◽

Burkhard König

Keyword(s):

Visible Light ◽

Vinyl Acetate ◽

Organic Semiconductor ◽

Alkyl Halides ◽

Visible Light Photocatalysis ◽

Dicarbonyl Compounds ◽

Semiconductor Photocatalysis ◽

Type Coupling ◽

Styrene Derivatives ◽

Tertiary Alkyl

We report the synthesis of 1,4-dicarbonyl compounds and substituted alkenes (Mizoroki–Heck type coupling) starting from secondary and tertiary alkyl halides and vinyl acetate or styrene derivatives using visible-light photocatalysis.

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Electron affinities of a homologous series of tertiary alkyl radicals and their C–H bond dissociation energies (BDEs)

Tetrahedron ◽

10.1016/j.tet.2008.12.043 ◽

2009 ◽

Vol 65 (8) ◽

pp. 1655-1659 ◽

Cited By ~ 2

Author(s):

Panayiotis S. Petrou ◽

Athanassios V. Nicolaides

Keyword(s):

Homologous Series ◽

Bond Dissociation Energies ◽

Electron Affinities ◽

Alkyl Radicals ◽

Bond Dissociation ◽

Dissociation Energies ◽

Tertiary Alkyl

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ChemInform Abstract: Nickel-Catalyzed Carbon-Carbon Bond-Forming Reactions of Unactivated Tertiary Alkyl Halides: Suzuki Arylations.

ChemInform ◽

10.1002/chin.201326047 ◽

2013 ◽

Vol 44 (26) ◽

pp. no-no

Author(s):

Susan L. Zultanski ◽

Gregory C. Fu

Keyword(s):

Alkyl Halides ◽

Carbon Bond ◽

Bond Forming ◽

Carbon Carbon Bond ◽

Bond Forming Reactions ◽

Tertiary Alkyl

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Copper-catalyzed direct alkylation of heteroarenes

Chemical Science ◽

10.1039/c6sc05622a ◽

2017 ◽

Vol 8 (5) ◽

pp. 3465-3470 ◽

Cited By ~ 38

Author(s):

Cédric Theunissen ◽

Jianjun Wang ◽

Gwilherm Evano

Keyword(s):

Alkyl Radicals ◽

Alkyl Bromides ◽

Tertiary Alkyl

An efficient and broadly applicable process is reported for the direct alkylation of heteroarene C–H bonds, based on the copper-catalyzed addition of alkyl radicals generated from activated secondary and tertiary alkyl bromides to a range of arenes, and their benzo-fused derivatives.

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