Copper-Catalyzed Electrophilic Amination of Arylsilanes with Hydroxylamines

Abstract

A copper-catalyzed electrophilic amination of aryl[(2-hydroxymethyl)phenyl]dimethylsilanes with O-acylated hydroxylamines has been developed to afford the corresponding anilines in good yields. The catalytic reaction proceeds very smoothly under mild conditions and tolerates a wide range of functional groups.

Copper-Catalyzed Electrophilic Amination of Organolithiums Mediated by Recoverable Siloxane Transfer Agents

“…Based on the similarities between the reactive intermediate involved in siloxane-based cross-coupling reactions (alkoxide 1a , Scheme 1) and arylsilanes 2 , recently employed in electrophilic aminations reported by Miura and co-workers (Scheme 2), 8 we reasoned that we could intersect this reaction manifold via a siloxane transfer agent. Success would provide a valuable and practical method for the direct amination of organolithium compounds with electrophilic aminating reagents, such as N , N -dialkyl- O -benzoyl hydroxylamines.…”

Transition‐Metal‐Catalyzed Electrophilic Amination: Application of O‐Benzoylhydroxylamines in the Construction of the C−N Bond

“…Then they described an another Cu I ‐catalyzed electrophilic amination of aryl[(2‐hydroxymethyl)phenyl]dimethylsilanes with O ‐benzoylhydroxylamines (Scheme ) . The amination was performed smoothly under mild conditions to form the corresponding anilines in good yields, tolerating a diverse set of functional groups.…”

“…Then they described an another Cu I -catalyzed electrophilic amination of aryl[(2-hydroxymethyl)phenyl]dimethylsilanes with O-benzoylhydroxylamines( Scheme 30). [28] The amination was performed smoothly under mild conditions to form the corresponding anilines in good yields, tolerating ad iverse set of functional groups. It is worth mentioning that the high halogen compatibilityo ft he catalytic reaction allowed the synthesis of bromide-substituted arylamines, which also complemented the conventional Pd-based amination chemistry.M oreover, inaccessible secondary acyclica lkylamines (through the conventional Chan-Lam-type coupling) could be synthesized easily under these reaction conditions.…”

Cobalt‐Catalyzed Electrophilic Amination of Aryl‐ and Heteroarylzinc Pivalates with N‐Hydroxylamine Benzoates

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Aryl-and heteroarylzinc pivalates can be aminated with O-benzoylhydroxylamines at 25 8 8Cw ithin 2-4 hi nt he presence of 2.5-5.0 %CoCl 2 ·2 LiCl to furnish the corresponding tertiary arylated or heteroarylated amines in good yields. [3] This amination [4] has been extended to organometallic compounds derived from Mg, [3d] Zn, [5] Al, [6] B, [7] Si, [8] and Cu [9] by using Cu or Ni as catalysts.Despite the impressive progress made,the use of air-sensitive reagents,ligands,ortoxic Ni catalysts still represent drawbacks.R ecently,w er eported an ew class of highly functionalized organozinc reagents with enhanced airand moisture-stability. Over the past two decades,t he development of palladiumcatalyzed Buchwald-Hartwig nucleophilic aminations [2] allowed the facile synthesis of aryl amines.H owever,t hese reactions usually require expensive catalysts and ligands.

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“…Thus,h eteroarylzinc pivalates 1f-i were aminated with 2a in 80-95 %y ield (Table 2, entries [5][6][7][8]. Thus,h eteroarylzinc pivalates 1f-i were aminated with 2a in 80-95 %y ield (Table 2, entries [5][6][7][8].…”