Metal-Catalyzed and Metal-Free Intermolecular Amination of Light Alkanes and Benzenes

Stavropoulos, Pericles

doi:10.1080/02603594.2016.1183487

Cited by 10 publications

(13 citation statements)

References 170 publications

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“…Itami's reviews on catalytic aromatic C-H amination reactions, [30,31] Shi's review on transition metalcatalyzed C(sp 3 )-H amination adjacent to double bonds and carbonyl groups [32] and Stavropoulos' review on intermolecular amination of light alkanes and benzenes. [33] Readers are encouraged to read these articles to get pertinent information. Cytochrome P450s can perform selective C-H bond hydroxylation under mild conditions, wherein reactive heme-based ironoxo species (FeO) are the key intermediates for C-H bond activation.…”

Section: Introductionmentioning

confidence: 99%

Recent Advances in Iron‐Catalyzed C—H Bond Amination via Iron Imido Intermediate

Wang

Deng

2018

Chin. J. Chem.

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Transition‐metal‐catalyzed C—H bond amination reaction is an attractive method for the synthesis of amines. Fueled by the growing interests in the development of economical and eco‐friendly catalysts for organic transformations, there are great recent efforts on developing iron‐catalyzed C—H bond amination reactions using organic azides, sulfonyl azides, and iminoiodanes as nitrene source. This review summarizes the progress achieved in the field since 2011. The reaction scope, the synthetic utility of the catalytic reaction, and the current mechanistic understandings of the C—H bond amination reactions catalyzed by hemoproteins, iron porphyrins and phthalocyanines, non‐heme‐type iron complexes, as well as metal‐organic‐ framework‐supported iron complexes are introduced and discussed.

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Section: Introductionmentioning

confidence: 99%

Recent Advances in Iron‐Catalyzed C—H Bond Amination via Iron Imido Intermediate

Wang

Deng

2018

Chin. J. Chem.

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“…We have also shown that PhI=NNs acts as a better nitrene source than its analog PhI=NTs for the arene CÀ H amination. 19 F NMR chemical shifts were referenced relative to external CFCl 3 . We have also demonstrated that it is possible to achieve reasonable yields of nitrene insertion products using equimolar amounts of aminating agent and the aromatic substrate.…”

Section: Full Papersmentioning

confidence: 99%

“…[2,3,[17][18][19] Considering their fundamental importance and synthetic value, significant effort has been devoted to the development of such direct arene CÀ H amination chemistry resulting in several important findings. [2,3,[17][18][19] Considering their fundamental importance and synthetic value, significant effort has been devoted to the development of such direct arene CÀ H amination chemistry resulting in several important findings.…”

Section: Introductionmentioning

confidence: 99%

“…Catalytic methods for the direct functionalization of inert arene CÀ H bonds leading to C(sp 2 )À N moieties have advantages over classical nitration/hydrogenation pathways or currently preferred cross-coupling chemistry in terms of step-efficiency and environmental considerations. [2,3,[17][18][19] Considering their fundamental importance and synthetic value, significant effort has been devoted to the development of such direct arene CÀ H amination chemistry resulting in several important findings. [2,17,[19][20][21] Intramolecular CÀ H amination processes, and those that rely on the use of directing groups or involve activated CÀ H bonds are more common.…”

Section: Introductionmentioning

confidence: 99%

“…[2,3,[17][18][19] Considering their fundamental importance and synthetic value, significant effort has been devoted to the development of such direct arene CÀ H amination chemistry resulting in several important findings. [2,17,[19][20][21] Intramolecular CÀ H amination processes, and those that rely on the use of directing groups or involve activated CÀ H bonds are more common. [22][23][24][25] In contrast, intermolecular, arene CÀ H functionalization chemistry of simple arenes such as benzene, mesitylene, etc., is particularly challenging.…”

Section: Introductionmentioning

confidence: 99%

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Nitrene Insertion into Aromatic and Benzylic C−H Bonds Catalyzed by Copper Complexes of Fluorinated Bis‐ and Tris(pyrazolyl)borates

et al. 2019

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Fluorinated bis-and tris(pyrazolyl)boratocopper complexes catalyze the nitrene insertion to CÀ H bonds of aromatic hydrocarbons efficiently producing amination products in good to excellent yields at room temperature. Imidoiodanes, PhI=NTs (Ts = p-toluenesulfonyl) and PhI=NNs (Ns = p-nitrophenylsulfonyl) serve as the nitrene source. The bis(pyrazolyl)borate catalyst [H 2 B(3,5-(CF 3 ) 2 Pz) 2 ]Cu(NCMe) with PhI=NNs produced the arene CÀ H functionalized product of mesitylene in 87 % yield with only trace amounts of benzylic CÀ H insertion. The use of [H 2 B (3,5-(CF 3 ) 2 -4-(NO 2 )Pz) 2 ]Cu(NCMe) that has an even weakly donating pyrazolate generated the arene CÀ H insertion product exclusively. The tris(pyrazolyl)borate complex [HB(3,5-(CF 3 ) 2 Pz) 3 ] Cu(NCMe), in contrast, generated the benzylic amination product from mesitylene and PhI=NNs in 82 % yield with only very minor amounts of arene CÀ H functionalization. DFT calculations suggest that Cu-nitrene moiety generated from [HB (3,5-(CF 3 ) 2 Pz) 3 ]Cu(NCMe) and PhI=NNs activates the benzylic CÀ H bond of mesitylene via a hydrogen atom abstraction (HAA) followed by a radical rebound (RR) pathway, whereas the functionalization of sp 2 CÀ H bonds of mesitylene by [H 2 B(3,5-(CF 3 ) 2 Pz) 2 ]Cu(NNs) ensues possibly via a nitrene addition to the arene core.[a] T.

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Rhodium(II)‐Catalyzed Selective C(sp³)−H Amination of Alkanes

Boquet,

Guimaraes Naves,

Brunard

et al. 2023

Eur J Org Chem

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The development of an efficient catalytic system enabling the conversion of alkanes to valuable nitrogen‐containing building blocks is reported. Light alkanes can be selectively functionalized by an intermolecular C(sp3)−H amination reaction that proceeds at room temperature in the presence of only 1 mol % of a dirhodium(II) complex. Selective amination of tertiary C(sp3)−H within acyclic or cyclic alkanes used as limiting components leads to the corresponding amides isolated with yields in the 51–96 % range. The reaction, that can be performed on a gram‐scale, applies with equal levels of efficiency and selectivity to more complex hydrocarbons.

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Metal-Catalyzed and Metal-Free Intermolecular Amination of Light Alkanes and Benzenes

Cited by 10 publications

References 170 publications

Recent Advances in Iron‐Catalyzed C—H Bond Amination via Iron Imido Intermediate

Recent Advances in Iron‐Catalyzed C—H Bond Amination via Iron Imido Intermediate

Nitrene Insertion into Aromatic and Benzylic C−H Bonds Catalyzed by Copper Complexes of Fluorinated Bis‐ and Tris(pyrazolyl)borates

Rhodium(II)‐Catalyzed Selective C(sp³)−H Amination of Alkanes

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Metal-Catalyzed and Metal-Free Intermolecular Amination of Light Alkanes and Benzenes

Cited by 10 publications

References 170 publications

Recent Advances in Iron‐Catalyzed C—H Bond Amination via Iron Imido Intermediate

Recent Advances in Iron‐Catalyzed C—H Bond Amination via Iron Imido Intermediate

Nitrene Insertion into Aromatic and Benzylic C−H Bonds Catalyzed by Copper Complexes of Fluorinated Bis‐ and Tris(pyrazolyl)borates

Rhodium(II)‐Catalyzed Selective C(sp3)−H Amination of Alkanes

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Rhodium(II)‐Catalyzed Selective C(sp³)−H Amination of Alkanes