A POCl3-mediated, direct amination reaction of heterocyclic amides/ureas with NH-heterocycles or N-substituted anilines is described. Compared to the existing methods, this operationally simple protocol provides unique reactivity and functional group compatibility because of the metal-free, acidic reaction conditions. The yields are generally excellent.
A facile synthesis of 1H-indazoles featuring a Cu(OAc)2-catalyzed N-N bond formation using oxygen as the terminal oxidant is described. The reaction of readily available 2-aminobenzonitriles with various organometallic reagents led to o-aminoaryl N-H ketimine species. The subsequent Cu(OAc)2-catalyzed N-N bond formation in DMSO under oxygen afforded a wide variety of 1H-indazoles in good to excellent yields.
An efficient synthesis of quinazolines based on an iron-catalyzed C(sp)-H oxidation and intramolecular C-N bond formation using tert-BuOOH as the terminal oxidant is described. The reaction of readily available 2-alkylamino benzonitriles with various organometallic reagents led to 2-alkylamino N-H ketimine species. The FeCl-catalyzed C(sp)-H oxidation of the alkyl group employing tert-BuOOH followed by intramolecular C-N bond formation and aromatization afforded a wide variety of 2,4-disubstituted quinazolines in good to excellent yields.
An efficient, one-pot and metal-free process for the preparation of 3,5-disubstituted and 3,4,5-trisubstituted pyrazoles on multi-gram scale was developed. One-pot condensation of ketones, aldehydes and hydrazine monohydrochloride readily formed pyrazoline intermediates under mild conditions. Oxidation of pyrazolines, in situ, employing bromine afforded a wide variety of pyrazoles. The methodology offers a fast, and often chromatography-free protocol for the synthesis of 3,4,5-substituted pyrazoles in good to excellent yields. Alternatively, a more benign oxidation protocol affords 3,5-disubstituted or 3,4,5-trisubstituted pyrazoles by simply heating pyrazolines in DMSO under oxygen.
A facile, one‐pot synthesis of 1H‐indazoles featuring a Cu‐catalyzed C–H ortho‐hydroxylation and N–N bond‐formation sequence with the use of pure oxygen as the terminal oxidant was developed. The reaction of readily available 2‐arylaminobenzonitriles with various organometallic reagents led to ortho‐arylamino N–H ketimine species. Subsequent Cu‐catalyzed hydroxylation at the ortho position of the aromatic ring followed by N–N bond formation in DMSO under a pure‐oxygen atmosphere afforded a wide variety of 1‐(ortho‐hydroxyaryl)‐1H‐indazoles in good to excellent yields. This efficient method does not require the utilization of noble‐metal catalysts, elaborate directing groups, or privileged ligands.
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