Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents

Berman, Ashley M.; Johnson, Jeffrey S.

doi:10.1021/ja049474e

Cited by 288 publications

(102 citation statements)

References 18 publications

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“…Primary O ‐benzoyl hydroxylamines, however, worked poorly in the reaction. To address this shortcoming, we experimented with the transmetalation of intermediate 6 with zinc; pioneering work from Johnson has shown that arylzinc compounds can react with primary O ‐benzoyl hydroxylamines under copper catalysis to give secondary anilines 13. We were pleased to find that the addition of ZnCl 2 (0.5 equiv) to the reaction mixture was successful, enabling i PrNHOBz and CyNHOBz to be used as electrophiles in the reaction ( 7 k , 7 l ) in 44 and 46 % yield, respectively.…”

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confidence: 99%

Double Heteroatom Functionalization of Arenes Using Benzyne Three‐Component Coupling

2015

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Arynes participate in three‐component coupling reactions with N, S, P, and Se functionalities to yield 1,2‐heteroatom‐difunctionalized arenes. Using 2‐iodophenyl arylsulfonates as benzyne precursors, we could effectively add magnesiated S‐, Se‐, and N‐nucleophilic components to the strained triple bond. In the same pot, addition of electrophilic N, S, or P reagents and a copper(I) catalyst trapped the intermediate aryl Grignard to produce a variety of 1,2‐difunctionalized arenes.

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confidence: 99%

Double Heteroatom Functionalization of Arenes Using Benzyne Three‐Component Coupling

2015

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“…[15,17,21,22] However, electrophilic amination of organometallic reagents by R 1 R 2 N + synthons, [23][24][25][26][27][28][29][30][31] though conceptually feasible, has received much less attention. [32][33][34][35][36][37] The putative catalytic cycle of this transformation is illustrated in Scheme 1: (1) reaction of R 1 R 2 N À X (as an electrophile) with the metal catalyst (M 1 ) would introduce the amine group to the metal center to form R 1 R 2 N-M 1 -X; [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] (2) transmetalation of RM 2 (M 2 = B(OH) 2 ) with R 1 R 2 N-M 1 -X to furnish R 1 R 2 N-M 1 R; and (3) final reductive elimination to form the CÀN bond.The groups of Liebeskind and Johnson have studied this type of CÀN bond formation employing NÀO derivatives. [32][33][34][35][36][37] N-Chloroamides, though attractive because of the ease of preparation [49][50][51] and the high activities of the N À Cl bond, …”

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confidence: 99%

“…[32][33][34][35][36][37] The putative catalytic cycle of this transformation is illustrated in Scheme 1: (1) reaction of R 1 R 2 N À X (as an electrophile) with the metal catalyst (M 1 ) would introduce the amine group to the metal center to form R 1 R 2 N-M 1 -X; [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] (2) transmetalation of RM 2 (M 2 = B(OH) 2 ) with R 1 R 2 N-M 1 -X to furnish R 1 R 2 N-M 1 R; and (3) final reductive elimination to form the CÀN bond.…”

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confidence: 99%

Aryl Halide Tolerated Electrophilic Amination of Arylboronic Acids with N‐Chloroamides Catalyzed by CuCl at Room Temperature

et al. 2008

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Dedicated to Professor Xiyan Lu on the occasion of his 80th birthdayTransition-metal-catalyzed aryl C sp2 ÀN bond formation has been intensively studied over the past decade because of the importance of the amines and their derivatives in chemistry related fields.[1-9] The Pd-or Cu-catalyzed formation of anilines from electrophilic aryl halides and nucleophilic primary or secondary amines, pioneered by Buchwald and co-workers and Louie and Hartwig, as well as others, [10][11][12][13][14] is a hallmark reaction in this field. In 1998, Chan et al., Evans et al., and Lam et al. independently developed Cu-mediated oxidative amination of nucleophilic arylboronic acids with amines or other nucleophiles, [16][17][18][19][20] and the methods were later improved to include catalytic versions. [15,17,21,22] However, electrophilic amination of organometallic reagents by R 1 R 2 N + synthons, [23][24][25][26][27][28][29][30][31] though conceptually feasible, has received much less attention. [32][33][34][35][36][37] The putative catalytic cycle of this transformation is illustrated in Scheme 1: (1) reaction of R 1 R 2 N À X (as an electrophile) with the metal catalyst (M 1 ) would introduce the amine group to the metal center to form R 1 R 2 N-M 1 -X; [34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] (2) transmetalation of RM 2 (M 2 = B(OH) 2 ) with R 1 R 2 N-M 1 -X to furnish R 1 R 2 N-M 1 R; and (3) final reductive elimination to form the CÀN bond.The groups of Liebeskind and Johnson have studied this type of CÀN bond formation employing NÀO derivatives. [32][33][34][35][36][37] N-Chloroamides, though attractive because of the ease of preparation [49][50][51] and the high activities of the N À Cl bond, [23,50,51] have seldom been utilized in catalytic electrophilic amination reactions. To the best of our knowledge, Göttlich et al. has primarily studied the Cu-mediated reaction of N-chloroamines with alkenes. [38,39,52] Herein, we communicate our results regarding ligandless copper-catalyzed electrophilic amination of arylboronic acids by N-chloroamides under mild conditions.Our initial experiments of N-chloro-N-phenylacetamide [49] (1 a) and phenylboronic acid (2 a) were carried out by using palladium catalysts. In all attempts, biphenyl was formed instead of the desired N-arylation product (3 a).

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“…Reported bases for this transformation include sodium carbonate, 22 sodium hydroxide, 24 tertbutylamine 25 and disodium hydrogen phosphate. 26 Pleasingly, caesium carbonate was found to be effective in the reaction of primary amines with benzoyl peroxide allowing for the direct conversion of primary amines to ketones. Treatment of a cooled DMF solution of caesium carbonate (1.5 equivalents) and benzoyl peroxide (1 equivalent) with the primary amine (1.2 equivalents) followed by warming of the reaction mixture led directly to the corresponding ketone ( Table 3).…”

Section: Methodsmentioning

confidence: 99%

Oxidation of Primary Amines to Ketones

Knowles¹,

Mathews²,

Tomkinson

2008

Synlett

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A simple method for the oxidation of primary amines to the corresponding ketones that proceeds in the presence of both moisture and air is described. Treatment of an amine with benzoyl peroxide in the presence of caesium carbonate, followed by warming of the hydroxylamine product to 50-70 °C leads directly to the ketone. The method is shown to be effective for both benzylic and aliphatic substrates.

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Copper-Catalyzed Electrophilic Amination of Diorganozinc Reagents

Cited by 288 publications

References 18 publications

Double Heteroatom Functionalization of Arenes Using Benzyne Three‐Component Coupling

Double Heteroatom Functionalization of Arenes Using Benzyne Three‐Component Coupling

Aryl Halide Tolerated Electrophilic Amination of Arylboronic Acids with N‐Chloroamides Catalyzed by CuCl at Room Temperature

Oxidation of Primary Amines to Ketones

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