Umpolung Amination: Nickel-Catalyzed Coupling Reactions of N,N-Dialkyl-N-chloroamines with Diorganozinc Reagents

Abstract

N,N-dialkyl-N-chloroamines are an effective source of electrophilic nitrogen for nickel-catalyzed coupling with diarylzinc reagents. A variety of N-chloroamines as well as organozinc reagents react smoothly under the reaction conditions. A one-pot procedure that circumvents the need to isolate the N-chloroamines is described.

Efficient catalytic aryl amination of bromoarenes using 3-iminophosphine palladium(II) chloride

“…N-(tert-butyl)aniline (Table 2, entry 1H) [45]; N-(tert-butyl)-4-methylaniline (Table 2, entry 1Me) [46]; N-(tert-butyl)-4-methoxyaniline (Table 2, entry 1MeO) [47]; N-(n-butyl)aniline ( Table 2, entry 2H) [48]; N-(n-butyl)-4-methylaniline (Table 2, entry 2Me) [48]; N-phenyl-2-aminooctane ( Table 2, entry 3H) [49]; N-(4-methylphenyl)-2-aminooctane ( Table 2, entry 3Me) [49]; N-(4- methoxyphenyl)-2-aminooctane (Table 2, entry 3MeO) [49]; N-(phenyl)octylamine (Table 2, entry 4H) [50]; N-(4-methylphenyl) octylamine (Table 2, entry 4Me) [51]; N-(4-methoxyphenyl)octylamine (Table 2, entry 4MeO) [52]; N,N-diethylaniline (Table 2, entry 5H) [53]; N,N-diethyl-4-methylaniline (Table 2, entry 5Me) [54]; N-butyl,Nmethylaniline (Table 2, entry 6H) [55]; N-butyl,N-methyl-4-methylaniline (Table 2, entry 6Me) [56]; N-butyl,N-methyl-4-methoxyaniline (Table 2, entry 6MeO) [56]; N,N-di-n-butylaniline (Table 2, entry 7H) [52]; N,N-di-n-butyl-4-methylaniline (Table 2, entry 7Me) [57]; N,N-di-n-butyl-4-methoxyaniline (Table 2, entry 7MeO) [55]; N,N-dicyclohexylaniline (Table 2, entry 8H) [53]; cyclohexyldiph...…”

Diaryl and Heteroaryl Sulfides: Synthesis via Sulfenyl Chlorides and Evaluation as Selective Anti-Breast-Cancer Agents

“…Recently, expansion of the scope of this reaction to include Grignard reagents was reported by Lee and co-workers (Figure 2c). 16 Contemporaneously, on the basis of our work with N -chloroamines, 17,18 we developed sulfenylation of organozinc reagents as a functional-group tolerant 19 strategy for synthesis of diaryl sulfides.…”

Rapid heteroatom transfer to arylmetals utilizing multifunctional reagent scaffolds

“…For example, primary anilines (that is, Ar–NH 2 ) and phenols (that is, Ar–OH) are used as intermediates or building blocks for the preparation of drug candidates, azo dyes and polyanilines 1,2 . Today, anilines are mostly prepared via one of the following methods: (1) the reduction of aromatic nitro compounds 3 ; (2) transition-metal-catalysed (Pd, Ni or Cu) cross-coupling of haloarenes and arylboronic acids with ammonia or substituted primary and secondary amines 4–7 , (3) transition-metal-catalysed (Pd, Ni or Cu) electrophilic amination of various organometallics 8–11 (for example, Li, Zn and B), (4) nucleophilic aromatic substitution (S N Ar) and nucleophilic substitution of hydrogen in electron-deficient systems 12–15 and (5) direct C–H amination 16 of aromatic rings. Phenols are often prepared via the following methods: (1) S N Ar in heteroaromatic systems 1,14,15,17 , (2) oxidation of arylboronic acids and derivatives 18 and (3) metal-catalysed direct hydroxylation of aromatic rings 19,20 .…”