280116-82-7Relevant articles and documents
Zinc-Catalyzed N-Alkylation of Aromatic Amines with Alcohols: A Ligand-Free Approach
Sankar, Velayudham,Kathiresan, Murugavel,Sivakumar, Bitragunta,Mannathan, Subramaniyan
supporting information, p. 4409 - 4414 (2020/09/01)
An efficient zinc-catalyzed N-alkylation reaction of aromatic amines was achieved using aliphatic, aromatic, and heteroaromatic alcohols as the alkylating reagent. A variety of aniline derivatives, including heteroaromatic amines, underwent the N-alkylation reaction and furnished the corresponding monoalkylated products in good to excellent yields. The application of the reaction is also further demonstrated by the synthesis of a 2-phenylquinoline derivative from acetophenone and 2-aminobenzyl alcohol. Deuterium labeling experiments show that the reaction proceeds via a borrowing hydrogen process. (Figure presented.).
Bidentate geometry-constrained iminopyridyl nickel-catalyzed synthesis of amines or imines via borrowing hydrogen or dehydrogenative condensation
Jiang, Yong,Hu, Miao,Sun, Nan,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan,Jin, Liqun
supporting information, (2020/11/27)
The efficient Ni-catalyzed N-alkylation of various anilines with alcohols via borrowing hydrogen is reported using a bidentate geometry-constrained iminopyridyl nickel complex as the catalyst. Substituted benzylic alcohols and short/long chain aliphatic alcohols could be applied as the alkylation sources to couple with aromatic and heteroaromatic amines to give a diverse set of N-alkylation outcomes in moderate to excellent yields. The nickel catalytic system was also suitable for aliphatic amines, selectively delivering the corresponding imines via an acceptorless dehydrogenative condensation strategy.
Copper-catalyzed direct amination of benzylic hydrocarbons and inactive aliphatic alkanes with arylamines
Jin, Shengzhou,Lin, Sen,Xie, Bo,Yan, Zhaohua,Yao, Hua,Zhong, Xiaoyang
supporting information, p. 3263 - 3268 (2020/05/14)
A new synthetic method toward direct C-N bond formation through saturated C-H amination of benzylic hydrocarbons and inactive aliphatic alkanes with primary aromatic amines under an inexpensive catalyst/oxidant (Cu/DTBP) system has been developed. Both aminopyridines and anilines could react smoothly with primary and secondary benzylic C-H substrates or cyclohexane to form the corresponding aromatic secondary amines in moderate to good yields. This protocol has the advantages of wide functional group tolerance and use of readily available raw materials.
An Efficient and Selective Nickel-Catalyzed Direct N-Alkylation of Anilines with Alcohols
Vellakkaran, Mari,Singh, Khushboo,Banerjee, Debasis
, p. 8152 - 8158 (2017/12/08)
Herein, we developed an efficient and selective nickel-catalyzed monoalkylation of various primary alcohols with aryl and heteroaryl amines together with diols and amino alcohol derivatives. Notably, the catalytic protocol consisting of an earth-abundant and non-precious NiBr2/L1 system enables the transformations in the presence of hydroxyl, alkene, nitrile, and nitro functionalities. As a highlight, we have demonstrated the alkylation of diamine, intramolecular cyclization to N-heterocycles, and functionalization of complex vitamin E, an (±)-α-tocopherol derivative. Preliminary mechanistic studies revealed the participation of a benzylic C-H bond in the rate-determining step.
Efficient and practical catalyst-free-like dehydrative N-alkylation of amines and sulfinamides with alcohols initiated by aerobic oxidation of alcohols under air
Li, Xiaohui,Li, Shuangyan,Li, Qiang,Dong, Xu,Li, Yang,Yu, Xiaochun,Xu, Qing
supporting information, p. 264 - 272 (2015/12/30)
We developed simple and practical N-alkylation reactions of amines and sulfinamides with primary and secondary alcohols by using only catalytic amounts of air as the initiator without adding any external catalysts. This method has advantages of simple conditions, easy operation, and comparatively wider scope of substrates, providing an efficient and green catalyst-free-like alcohol-based dehydrative N-alkylation method. Mechanistic studies revealed that air initiated the reactions by aerobic oxidation of the alcohols to the key initiating aldehydes or ketones in the presence of bases.
Manganese dioxide catalyzed N-alkylation of sulfonamides and amines with alcohols under air
Yu, Xiaochun,Liu, Chuanzhi,Jiang, Lan,Xu, Qing
supporting information; experimental part, p. 6184 - 6187 (2012/01/06)
By simply running the reactions under air and solvent-free conditions using catalytic amounts of manganese dioxide, a practical and efficient N-alkylation method for a variety of sulfonamides and amines using alcohols as green alkylating reagents was developed.
Discovery and mechanistic studies of a general air-promoted metal-catalyzed aerobic n- alkylation reaction of amides and amines with alcohols
Liu, Chuanzhi,Liao, Shiheng,Li, Qiang,Feng, Sunlin,Sun, Qing,Yu, Xiaochun,Xu, Qing
supporting information; scheme or table, p. 5759 - 5773 (2011/09/16)
The thermodynamically unfavorable anaerobic dehydrogenative alcohol activation to aldehydes and hydridometal species is found to be the bottleneck in metal-catalyzed N-alkylations due to a general and unnoticed catalyst deactivation by amines/amides. Thus, different from the anaerobic dehydrogenation process in borrowing hydrogen or hydrogen autotransfer reactions that require noble metal complexes or addition of capricious ligands for catalyst activation, the water-producing, exothermic, metal-catalyzed aerobic alcohol oxidation is thermodynamically more favorable and the most effective and advantageous aldehyde generation protocol. This leads to a general and advantageous air-promoted metal-catalyzed aerobic N-alkylation methodology that effectively uses many simpler, less expensive, more available, and ligand-free metal catalysts that were inactive under typical anaerobic borrowing hydrogen conditions, avoiding the use of preformed metal complexes and activating ligands and the exclusive requirement of inert atmosphere protection. This aerobic method is quite general in substrate scope and tolerates various amides, amines, and alcohols, revealing its potentially broad utilities and interests in academy and industry. In contrast to the commonly accepted borrowing hydrogen mechanism, based on a thorough mechanistic study and supported by the related literature background, a new mechanism analogous to the relay race game that has never been proposed in metal-catalyzed N-alkylation reactions is presented.
Pyridinium N-,(2'-azinyl)aminides: Regioselective synthesis of 2- alkylaminoazines
Martínez-Barrasa, Valentín,Delgado, Francisca,Burgos, Carolina,Luis García-Navío,Luisa Izquierdo,Alvarez-Builla, Julio
, p. 2481 - 2490 (2007/10/03)
The regioselective alkylation of pyridinium-N-(2f'-azinil)aminides with alkyl halides under mild conditions is described. The alkylation, combined with a reduction of the N-N bond, allows an easy preparation of 2- alkylaminoazines. (C) 2000 Elsevier Science Ltd.
