ChemInform Abstract: [FeIII(F20-tpp)Cl] Is an Effective Catalyst for Nitrene Transfer Reactions and Amination of Saturated Hydrocarbons with Sulfonyl and Aryl Azides as Nitrogen Source under Thermal and Microwave-Assisted Conditions.

Terminal copper-nitrenoid complexes have inspired interest in their fundamental bonding structures as well as their putative intermediacy in catalytic nitrene-transfer reactions. Here, we report that aryl azides react with a copper(I) dinitrogen complex bearing a sterically encumbered dipyrrin ligand to produce terminal copper nitrene complexes with near-linear, short copper–nitrenoid bonds [1.745(2) to 1.759(2) angstroms]. X-ray absorption spectroscopy and quantum chemistry calculations reveal a predominantly triplet nitrene adduct bound to copper(I), as opposed to copper(II) or copper(III) assignments, indicating the absence of a copper−nitrogen multiple-bond character. Employing electron-deficient aryl azides renders the copper nitrene species competent for alkane amination and alkene aziridination, lending further credence to the intermediacy of this species in proposed nitrene-transfer mechanisms.

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Synthesis and catalytic activity of μ-oxo ruthenium(IV) porphyrin species to promote amination reactions

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424616500814 ◽

2016 ◽

Vol 20 (08n11) ◽

pp. 1156-1165 ◽

Cited By ~ 5

Author(s):

Paolo Zardi ◽

Daniela Intrieri ◽

Daniela Maria Carminati ◽

Francesco Ferretti ◽

Piero Macchi ◽

...

Keyword(s):

Molecular Structure ◽

Catalytic Activity ◽

Single Crystal ◽

General Formula ◽

Catalytic Efficiency ◽

Transfer Reactions ◽

Aryl Azides ◽

X Ray ◽

Nitrene Transfer ◽

Catalytically Active

This work describes the synthesis of ruthenium(IV) [Formula: see text]-oxo porphyrin complexes of general formula [RuIV(TPP)(X)]2O which have been applied as catalysts in nitrene transfer reactions using aryl azides (ArN[Formula: see text] as nitrene sources. Collected data indicated that the catalytic efficiency of [RuIV(TPP)(OCH[Formula: see text]]2O was comparable to that of RuII(TPP)CO because of their analogous reactivity towards aryl azides to give the same catalytically active bis-imido species RuVI(TPP)(ArN)2. The reaction of [RuIV(TPP)(OCH[Formula: see text]]2O with Ph3CN3 or (CH[Formula: see text]SiN3 afforded [RuIV(TPP)(N[Formula: see text]]2O which was fully characterised, its molecular structure was also determined by single crystal X-ray analysis.

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A combined experimental and theoretical study on the reactivity of nitrenes and nitrene radical anions

Nature Communications ◽

10.1038/s41467-021-27687-6 ◽

2022 ◽

Vol 13 (1) ◽

Author(s):

Yujing Guo ◽

Chao Pei ◽

Rene M. Koenigs

Keyword(s):

Radical Anion ◽

Room Temperature ◽

Theoretical Study ◽

Transition Metal Catalysts ◽

Transfer Reactions ◽

Mechanistic Studies ◽

Reaction Conditions ◽

Nitrene Transfer ◽

Triplet Nitrene ◽

Nitrogen Bonds

AbstractNitrene transfer reactions represent one of the key reactions to rapidly construct new carbon-nitrogen bonds and typically require transition metal catalysts to control the reactivity of the pivotal nitrene intermediate. Herein, we report on the application of iminoiodinanes in amination reactions under visible light photochemical conditions. While a triplet nitrene can be accessed under catalyst-free conditions, the use of a suitable photosensitizer allows the access of a nitrene radical anion. Computational and mechanistic studies rationalize the access and reactivity of triplet nitrene and nitrene radical anion and allow the direct comparison of both amination reagents. We conclude with applications of both reagents in organic synthesis and showcase their reactivity in the reaction with olefins, which underline their markedly distinct reactivity. Both reagents can be accessed under mild reaction conditions at room temperature without the necessity to exclude moisture or air, which renders these metal-free, photochemical amination reactions highly practical.

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Iron-Catalyzed C–H Functionalization Reactions via Carbene and Nitrene Transfer Reactions

Iron Catalysis - Catalytic Science Series ◽

10.1142/9781786349620_0007 ◽

2021 ◽

pp. 203-252

Author(s):

Claire Empel ◽

Sripati Jana ◽

Rene M. Koenigs

Keyword(s):

Transfer Reactions ◽

Nitrene Transfer

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Light-Induced Ruthenium-Catalyzed Nitrene Transfer Reactions: A Photochemical Approach towards N-Acyl Sulfimides and Sulfoximines

Angewandte Chemie ◽

10.1002/ange.201310790 ◽

2014 ◽

Vol 126 (22) ◽

pp. 5745-5748 ◽

Cited By ~ 37

Author(s):

Vincent Bizet ◽

Laura Buglioni ◽

Carsten Bolm

Keyword(s):

Transfer Reactions ◽

Nitrene Transfer

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Iron-Catalyzed Nitrene Transfer Reaction of 4-Hydroxystilbenes with Aryl Azides: Synthesis of Imines via C═C Bond Cleavage

Organic Letters ◽

10.1021/acs.orglett.9b03160 ◽

2019 ◽

Vol 21 (20) ◽

pp. 8389-8394 ◽

Cited By ~ 1

Author(s):

Yi Peng ◽

Yan-Hui Fan ◽

Si-Yuan Li ◽

Bin Li ◽

Jing Xue ◽

...

Keyword(s):

Transfer Reaction ◽

Bond Cleavage ◽

Aryl Azides ◽

Nitrene Transfer

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Hydrogen transfer reactions. I. Reduction of carbonyl compounds by alcohols catalyzed by alumina

Canadian Journal of Chemistry ◽

10.1139/v69-616 ◽

1969 ◽

Vol 47 (19) ◽

pp. 3705-3707 ◽

Cited By ~ 21

Author(s):

D. V. Ramana ◽

C. N. Pillai

Keyword(s):

Vapor Phase ◽

Carbonyl Compounds ◽

Hydrogen Transfer ◽

Isopropyl Alcohol ◽

Aromatic Aldehydes ◽

Transfer Reactions ◽

Secondary Alcohols ◽

Effective Catalyst ◽

Phase Reduction ◽

Aldehydes And Ketones

Alumina containing about 2.2% by weight of Na+ has been found to be an effective catalyst for the vapor phase reduction of carbonyl compounds by alcohols and for the reverse reaction, the oxidation of the alcohols by carbonyl compounds. The reduction of a number of aliphatic and aromatic aldehydes and ketones by isopropyl alcohol and the oxidation of a number of primary and secondary alcohols by ketones like acetone and cyclohexanone are reported.

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