195191-58-3Relevant articles and documents
Indoles from o-haloanilines: Syntheses of tryptamines and tryptophols via regioselective hydroformylation of functionalized anilines
Dong,Busacca
, p. 6464 - 6465 (1997)
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Coupling N-H Deprotonation, C-H Activation, and Oxidation: Metal-Free C(sp3)-H Aminations with Unprotected Anilines
Evoniuk, Christopher J.,Gomes, Gabriel Dos Passos,Hill, Sean P.,Fujita, Satoshi,Hanson, Kenneth,Alabugin, Igor V.
, p. 16210 - 16221 (2017/11/22)
An intramolecular oxidative C(sp3)-H amination from unprotected anilines and C(sp3)-H bonds readily occurs under mild conditions using t-BuOK, molecular oxygen and N,N-dimethylformamide (DMF). Success of this process, which requires mildly acidic N-H bonds and an activated C(sp3)-H bond (BDE 85 kcal/mol), stems from synergy between basic, radical, and oxidizing species working together to promote a coordinated sequence of deprotonation: H atom transfer and oxidation that forges a new C-N bond. This process is applicable for the synthesis of a wide variety of N-heterocycles, ranging from small molecules to extended aromatics without the need for transition metals or strong oxidants. Computational results reveal the mechanistic details and energy landscape for the sequence of individual steps that comprise this reaction cascade. The importance of base in this process stems from the much greater acidity of transition state and product for the 2c,3e C-N bond formation relative to the reactant. In this scenario, selective deprotonation provides the driving force for the process.
Facile synthesis of biologically active heterocycles by indium-induced reactions of aromatic nitro compounds in aqueous ethanol
Banik, Bimal K.,Banik, Indrani,Samajdar, Susanta,Wilson, Mary
, p. 283 - 296 (2007/10/03)
Indium/ammonium chloride-induced reduction of aromatic nitro compounds to aromatic amines in aqueous ethanol was developed. Useful chemoselectivity was observed in the reduction reaction. This method was extended to reductive cyclization and rearrangement toward the synthesis of various biologically active heterocycles, including quinoline, oxazines, quinalonones, and phenanthridine in excellent yield. The oxophilicity of indium metal influenced the reaction in aqueous ethanol. Metals like zinc and tin were not effective in promoting this kind of reactions under the present environmentally friendly conditions.
