A Copper‐Catalyzed Decarboxylative Amination/Hydroamination Sequence: Switchable Synthesis of Functionalized Indoles

Li, Tianren; Cheng, Bei‐Yi; Wang, Yani; Zhang, Mao-Mao; Lu, Liang‐Qiu; Xiao, Wen‐Jing

doi:10.1002/ange.201605900

Cited by 28 publications

(4 citation statements)

References 60 publications

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“…An interesting cascade process has been observed from the reaction of cyclic carbamate 867 with indoline (868) in the presence of a copper catalyst ligated with bisoxazoline ligand 869 (Scheme 174). 421 Upon treatment with the copper catalyst, cyclic carbamate 867 is converted into a copper allenylidene complex via extrusion of CO 2 , which is then attacked by indoline to generate N-tosylaniline 871. Subsequently, the initial substitution product 871 is cyclized to bisindoline 872, likely through 5-exo addition of the N-Ts group to a copper π-alkyne intermediate.…”

Section: Catalytic Reactions Of Metal-complexed Allenylidenesmentioning

confidence: 99%

Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis

2019

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With their mechanistic novelty and various modalities of reactivity, transition metal unsaturated carbene (alkenylidene) complexes have emerged as versatile intermediates for new reaction discovery. In particular, the past decade has witnessed remarkable advances in the chemistry of metal vinylidenes and allenylidenes, leading to the evolution of a diverse array of new catalytic transformations that are mechanistically distinct from those developed in the previous two decades. This review aims to provide a survey of the recent achievements in the development of organic reactions that make use of transition metal alkenylidenes as catalytic intermediates and their applications to organic synthesis.

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Section: Catalytic Reactions Of Metal-complexed Allenylidenesmentioning

confidence: 99%

Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis

2019

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“…To this end, we are interested in cascade annulation reactions using 4-ethynyl benzoxazinanone [23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] . Xiao, Lu, and co-workers synthesized ethynyl benzoxazinanone in 2016.…”

mentioning

confidence: 99%

“…In the presence of suitable interceptors, various ethynyl-N-heterocycles can be constructed from 4-ethynyl benzoxazinanones in a similar fashion (Fig. 2b) [23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41] . That is, the intermolecular annulations start with an attack of the interceptor (Y − -Z + ) at the γ-position of Cuallenylidene intermediate I followed by the formation of the nitrogen-Z (N-Z) bond and the regeneration of the ethynyl moiety.…”

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confidence: 99%

Construction of poly-N-heterocyclic scaffolds via the controlled reactivity of Cu-allenylidene intermediates

et al. 2021

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Controlling the sequence of the three consecutive reactive carbon centres of Cu-allenylidene remains a challenge. One of the impressive achievements in this area is the Cu-catalyzed annulation of 4-ethynyl benzoxazinanones, which are transformed into zwitterionic Cu-stabilized allenylidenes that are trapped by interceptors to provide the annulation products. In principle, the reaction proceeds via a preferential γ-attack, while annulation reactions via an α- or β-attack are infrequent. Herein, we describe a method for controlling the annulation mode, by the manipulation of a CF3 or CH3 substituent, to make it proceed via either a γ-attack or an α- or β-attack. The annulation of CF3-substituted substrates with sulfamate-imines furnished densely functionalized N-heterocycles with excellent enantioselectivity via a cascade of an internal β-attack and an external α-attack. CH3-variants were transformed into different heterocycles that possess a spiral skeleton, via a cascade of an internal β-attack and a hydride α-migration followed by a Diels−Alder reaction.

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“…Radical rearrangement and olefin addition led to the formation of radical 77. The intermediate 78 then underwent a copper-catalyzed decarboxylative reaction [26] to obtain 79. Subsequently, the anion 79 is oxidized to the radical 80, possibly under the work of Cu(II).…”

Section: Metal-catalyzed Decarboxylative Cyclizationmentioning

confidence: 99%

Heterocycle Synthesis via Decarboxylative Cyclization Methods

Wang

Qiu

et al. 2022

Adv Synth Catal

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Carboxylic acid compounds are important structural units that exist widely in nature; the only byproduct in the decarboxylation process is carbon dioxide, which is non‐flammable, non‐toxic, and easy to remove. Therefore, decarboxylative reactions are of great importance in synthetic chemistry. Heterocyclic compounds are important backbones that constitute a variety of biologically active molecules; therefore, research into the development of new synthetic tactics for heterocyclic derivatives based on decarboxylative cyclization is of great interest. In this paper, we describe metal‐catalyzed, visible light‐driven, electrochemically enabled, decarboxylative cyclization reactions, as well as other types, that have been rapidly developed in the past five years; moreover, for some of these methods, we discuss the scope of their application and the mechanism of the reaction.

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A Copper‐Catalyzed Decarboxylative Amination/Hydroamination Sequence: Switchable Synthesis of Functionalized Indoles

Cited by 28 publications

References 60 publications

Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis

Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis

Construction of poly-N-heterocyclic scaffolds via the controlled reactivity of Cu-allenylidene intermediates

Heterocycle Synthesis via Decarboxylative Cyclization Methods

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