Direct Borylation of Tertiary Anilines via C–N Bond Activation

Abstract

The first successful catalytic borylation of unactivated aromatic C-N bonds of tertiary anilines without the preactivation or any directing groups is demonstrated. The reactivity of both N,N-dialkylarylamines and N-arylpyrroles were investigated systematically, and the targeted products were furnished in moderate to good yields. The DFT calculation results indicated that the catalytic cycle is furnished via a five-membered cyclic transition-state due to the steric hindrance of the Ni/NHC catalytic system.

Nickel(II)-Catalyzed Borylation of Alkenyl Methyl Ethers via C–O Bond Cleavage

“…Arylamines were also compatible under these conditions. Although nickel-catalyzed borylation of tertiary anilines via C–N bond activation was reported by Shi’s group, 2g with a dimethylamino group was obtained in 88% yield . Other electron-donating substrates such as 1h could convert to biphenyl alkenyl boronic ester 2h in 76% yield under this conditions.…”

Photoinduced Deaminative Borylation of Unreactive Aromatic Amines Enhanced by CO2

“…The first example of C–N transformation without the use of a directing group was reported by Shi et al (Scheme , b-2). They developed Ni-catalyzed direct C–N borylation and arylation of tertiary anilines. Direct C–N transformations have generally been catalyzed by transition metal complexes via oxidative addition of the C–N bonds to the metal center. , However, metal-free direct transformations of unreactive aromatic C–N bonds are yet to be developed.…”

Photoinduced Deaminative Borylation of Unactivated Aromatic Amines Enhanced by CO2

“…The first example of C-N transformation without the use of a directing group was reported by Shi et al (Scheme 1, b-2). They developed Ni-catalyzed direct C-N borylation 20 and arylation 21 of tertiary anilines. Direct C-N transformations have generally been catalyzed by transition metal complexes via oxidative addition of the C-N bonds to the metal center.…”