Catalytic insertion of diazo compounds into N–H bonds: the copper alternative

Morilla, M. Esther; Díaz‐Requejo, M. Mar; Belderraín, Tomás R.; Nicasio, M. Carmen; Trofimenko, Swiatoslaw; Pérez, Pedro J.

doi:10.1039/b207389g

Cited by 94 publications

(37 citation statements)

References 28 publications

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“…In the case of copper, the first observation of one of these species under catalytic conditions is due to Straub and Hofmann. [5] Later, Warren and Dai described the preparation and structural characteriza- [ [6] In recent years we have described the potential of a family of complexes of general formula [Tp x Cu(NCMe)] (Tp x = homoscorpionate ligand) toward the two processes mentioned above: the addition of :CHCO 2 Et from ethyl diazoacetate (EDA) to multiple carbon-carbon bonds (alkenes, [7] alkynes, [8] aromatics [9] ) or its insertion into single X-H bonds (alkanes, [10] amines, [11] alcohols [12] ). All these transformations are accompanied by the copper-catalyzed carbene coupling reaction, which leads to the formation of diethyl fumarate and maleate in variable yields [Equation (1)].…”

Section: Introductionmentioning

confidence: 99%

The Effect of Catalyst Loading in Copper‐Catalyzed Cyclohexane Functionalization by Carbene Insertion

et al. 2007

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A study of the variables that affect the insertion of the :CHCO2Et group (formed from ethyl diazocetate, EDA) into the C–H bonds of cyclohexane in the presence of a TpxCu complex as the catalyst (Tpx = trispyrazolylborate ligand) has demonstrated an anomalous effect of the catalyst loading. The use of low concentrations of catalyst produces an increase in the yield of the C–H activation product ethyl cyclohexaneacetate. This effect has also been found in the case of other less elaborated catalysts such as [BpBr3Cu] or [(bipy)2Cu][I]. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Section: Introductionmentioning

confidence: 99%

The Effect of Catalyst Loading in Copper‐Catalyzed Cyclohexane Functionalization by Carbene Insertion

et al. 2007

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“…Notably, the catalytic carbene insertion into NÀH bonds was observed with amines in a previous work from our laboratory. [9] The interaction of the metallocarbene intermediate with the NÀH bond probably occurs through the N-lone pair. Therefore, we do not consider this byproduct in the mechanistic studies.…”

Section: Resultsmentioning

confidence: 99%

Catalytic Functionalization of Indoles by Copper‐Mediated Carbene Transfer

Delgado-Rebollo¹,

Prieto²,

Pérez³

2014

ChemCatChem

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The complex [TpBr3Cu(NCMe)] (TpBr3=hydrotris(3,4,5‐tribromo)pyrazolylborate) efficiently catalyzes the CH functionalization of indole derivatives at C3 by carbene transfer from different diazoesters in a high‐yield transformation involving low catalyst loadings and short reaction times. This system has shown that the previously proposed dichotomy of carbene addition (to the double bond) vs carbene insertion (to the CH bond) corresponds to two consecutive reaction steps: the cyclopropane intermediates, observed in the reaction mixtures, are the precursors of the final CH functionalization derivatives in a ring‐opening process involving acid catalysis. Those in situ generated cyclopropanes undergo nucleophilic ring opening with Me2CuLi to afford both C2 and C3 functionalized indoles.

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“…But this reaction also gave a 66% yield of 15 even in the absence of the gold catalyst under the same conditions. Although this reaction has been reported to be catalyzed by complexes of Ru, Fe, and Cu [33][34][35][36][37][38][39][40][41][42][43][44][45], we are not aware of a previous report of the uncatalyzed reaction. …”

Section: Reactions Of Other Diazoalkanes and Aminesmentioning

confidence: 86%

“…4) when catalyzed by a variety of homogeneous transition metal complexes. For reviews involving catalyzed diazo compound N-H insertion reactions, see: [33][34][35][36][37][38][39][40][41][42][43][44]. For examples of highly enantioselective metal-catalyzed intermolecular carbenoid N-H insertion reactions, see: [45].…”

Section: Introductionmentioning

confidence: 99%

Bulk Gold-Catalyzed Reactions of Diazoalkanes with Amines and O2 to Give Enamines

2010

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Bulk gold powder, consisting of approximately 5-50 lm particles, catalyzes reactions of diazoalkanes E(H)C=N 2 , where E is CO 2 Et or PhC(O), with amines R 1 R 2 NH and O 2 to give enamine products (R 1 R 2 N) (E)C=CH(E) in 58-94% yield. The reactions are proposed to occur by initial formation of surface-bound (E)(H)C: carbene groups that are attacked by nucleophilic amines. The enamine products are very different than those obtained in reactions catalyzed by homogeneous transition metal complexes. These reactions of diazoalkanes, amines, and O 2 represent a new type of bulk gold-catalyzed reaction.

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Catalytic insertion of diazo compounds into N–H bonds: the copper alternative

Abstract: The complexes TpxCu (Tpx = homoscorpionate) catalyse the insertion of diazo compounds into nitrogen-hydrogen bonds of amines and amides, under very mild conditions, with quantitative yields being obtained with equimolar ratios of reactants.

Cited by 94 publications

References 28 publications

The Effect of Catalyst Loading in Copper‐Catalyzed Cyclohexane Functionalization by Carbene Insertion

The Effect of Catalyst Loading in Copper‐Catalyzed Cyclohexane Functionalization by Carbene Insertion

Catalytic Functionalization of Indoles by Copper‐Mediated Carbene Transfer

Bulk Gold-Catalyzed Reactions of Diazoalkanes with Amines and O2 to Give Enamines

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