Recent synthetic advances in the nucleophilic amination of benzenes

Belfield, Andrew J.; Brown, George R.; Foubister, Alan J.

doi:10.1016/s0040-4020(99)00668-7

Cited by 116 publications

(39 citation statements)

References 80 publications

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“…Thus, tetraarylated propane-1,3-diamine (51) and ethane-1,2-diamine (52) were obtained in remarkable 95% yields ( Table 5, entries 8,9), as well as the pentasubstituted triamine 53 and the tetrasubstituted product 54. Thus, tetraarylated propane-1,3-diamine (51) and ethane-1,2-diamine (52) were obtained in remarkable 95% yields ( Table 5, entries 8,9), as well as the pentasubstituted triamine 53 and the tetrasubstituted product 54.…”

Section: Polyarylation Of Polyaminesmentioning

confidence: 99%

“…(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) reactions of aryl halides. [9] Procedures involving nitration followed by hydrogenation are not tolerated by many functional groups and are often complicated due to the need for protection and deprotection steps. The direct nucleophilic substitution of aryl halides is a synthetic route dedicated only to substrates that contain electron-withdrawing groups, including perfluorinated compounds, [10,11] and Ullmann-type substitution reactions occur at high temperatures, giving generally diarylation products, and depend strongly on the nature of the substrate substituents.…”

Section: Introductionmentioning

confidence: 99%

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Palladium‐Catalyzed Arylation of Linear and Cyclic Polyamines

et al. 2005

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Synthetic protocols for the palladium-catalyzed arylation of various linear and cyclic polyamines and polyoxapolyamines has been worked out. Pd(0) and Pd(II) complexes with such phosphine ligands as dppf, BINAP, PPF-OMe, P(tBu) 3 , 2-ditert-butylphosphino-1,1′-biphenyl have been explored in the catalytic amination reactions. Monoamination of chloro-, bromo-, and iodoarenes with di-, tri-, and tetraamines have been carried out, conditions for di-and polyarylation of linear polyamines have been elaborated. Successful arylation of 1,4,7,10-tetraazacyclododecane (cyclene) and 1,4,8,11-tetraazacyclotetradecane (cyclam) have been conducted. Intramolecular diamination of dihaloarenes such as 1,2-dibromobenzene, 2,6-dichlorobromobenzene, 1,3-dibromobenzene, 1,8-dichloroanthracene, 1,8-dichloroanthraquinone, 1,5-dichloroanthracene, and 1,5-dichloroanthraquinone afforded corresponding polyazamacrocycles containing arene moieties. For the first time, a convenient one-pot synthesis of the face-to-face arranged bismacrocyclic systems has been carried out.

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Section: Polyarylation Of Polyaminesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Arylation of Linear and Cyclic Polyamines

et al. 2005

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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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“…These are important components in many biological active natural products, medicinally important compounds as well as in materials with useful electrical and mechanical properties [4][5][6]. High purity triarylamines find applications in xerographic photoreceptors as constituents of non linear optical chromophores useful in the design of integrated electro-optic switches and modulators, and as hole-transport materials for organic electroluminescent (EL) display devices [7].…”

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confidence: 99%