3074-43-9Relevant articles and documents
Mechanistic insights into the Pd(BINAP)-catalyzed amination of aryl bromides: Kinetic studies under synthetically relevant conditions
Singh, Utpal K.,Strieter, Eric R.,Blackmond, Donna G.,Buchwald, Stephen L.
, p. 14104 - 14114 (2002)
Kinetic studies using reaction calorimetry were carried out under synthetically relevant conditions to study the mechanism of the amination of bromobenzene with primary and secondary amines using Pd2(dba)3/BINAP mixtures as well as p
Mechanistic study of nucleophilic fluorination for the synthesis of fluorine-18 labeled fluoroform with high molar activity fromN-difluoromethyltriazolium triflate
Chai, Jin Young,Cha, Hyojin,Lee, Sung-Sik,Oh, Young-Ho,Lee, Sungyul,Chi, Dae Yoon
, p. 6099 - 6106 (2021/02/12)
The synthesis of fluorine-18 labeled fluoroform with high molar activity has grown in importance for the development of fluorine-18 labeled aryl-CF3radiopharmaceuticals that are useful as diagnostic radiotracers for the powerful technique of positron emission tomography (PET). We designed a strategy of synthesizing fluorine-18 labeled fluoroform fromN1-difluoromethyl-N3-methyltriazolium triflate (1)viaSN2 fluorination without stable fluorine isotope scrambling. Fluoroform was generated at rt in 10 min by fluorination of the triazolium precursor with TBAF (6 equiv.). We propose three routes (a), (b), and (c) for this fluorination. Quantum chemical calculations have been carried out to elucidate the mechanism of experimentally observed nucleophilic attack of fluoride at difluoromethyl groupviaroute (a), notN3-methylviaroute (b).1H and19F NMR studies using deuterium source have been performed to examine the competition between SN2 fluorination (route (a)) and the formation of difluorocarbene (route (c)). The observed superiority of SN2 pathway to formation of difluorocarbene in the reaction of the precursor using CsF in (CD3CN/(CD3)3COD (17.8?:?1)) gives the possibility of preparing the fluorine-18 labeled fluoroform in high molar activity.
1,4-Dioxane-Tuned Catalyst-Free Methylation of Amines by CO2 and NaBH4
Guo, Zhiqiang,Zhang, Bo,Wei, Xuehong,Xi, Chanjuan
, p. 2296 - 2299 (2018/07/31)
A catalyst-free reductive functionalization of CO2 with amines and NaBH4 was developed. The N-methylation of amines was carried out with CO2 as a C1 building block and 1,4-dioxane as the solvent. Notably, the six-electron reduction of CO2 to form the methyl group occurred simultaneously with formation of the C?N bond to give the N-methylated amine.
