1667-16-9Relevant articles and documents
Intramolecular C?H Amination of N-Alkylsulfamides by tert-Butyl Hypoiodite or N-Iodosuccinimide
Kiyokawa, Kensuke,Jou, Keisuke,Minakata, Satoshi
supporting information, p. 13971 - 13976 (2021/08/30)
1,3-Diamines are an important class of compounds that are broadly found in natural products and are also widely used as building blocks in organic synthesis. Although the intramolecular C?H amination of N-alkylsulfamide derivatives is a reliable method for the construction of 1,3-diamine structures, the majority of these methods involve the use of a transition-metal catalyst. We herein report on a new transition-metal-free method using tert-butyl hypoiodite (t-BuOI) or N-iodosuccinimide (NIS), enabling secondary non-benzylic and tertiary C?H amination reactions to proceed. The cyclic sulfamide products can be easily transformed into 1,3-diamines. Mechanistic investigations revealed that amination reactions using t-BuOI or NIS each proceed via different pathways.
Highly economical and direct amination of sp3carbon using low-cost nickel pincer catalyst
Brandt, Andrew,Rangumagar, Ambar B.,Szwedo, Peter,Wayland, Hunter A.,Parnell, Charlette M.,Munshi, Pradip,Ghosh, Anindya
, p. 1862 - 1874 (2021/01/20)
Developing more efficient routes to achieve C-N bond coupling is of great importance to industries ranging from products in pharmaceuticals and fertilizers to biomedical technologies and next-generation electroactive materials. Over the past decade, improvements in catalyst design have moved synthesis away from expensive metals to newer inexpensive C-N cross-coupling approaches via direct amine alkylation. For the first time, we report the use of an amide-based nickel pincer catalyst (1) for direct alkylation of amines via activation of sp3 C-H bonds. The reaction was accomplished using a 0.2 mol% catalyst and no additional activating agents other than the base. Upon optimization, it was determined that the ideal reaction conditions involved solvent dimethyl sulfoxide at 110 °C for 3 h. The catalyst demonstrated excellent reactivity in the formation of various imines, intramolecularly cyclized amines, and substituted amines with a turnover number (TON) as high as 183. Depending on the base used for the reaction and the starting amines, the catalyst demonstrated high selectivity towards the product formation. The exploration into the mechanism and kinetics of the reaction pathway suggested the C-H activation as the rate-limiting step, with the reaction second-order overall, holding first-order behavior towards the catalyst and toluene substrate.
Half-Sandwich Ru(II) Complexes with N,O-Chelate Ligands: Diverse Catalytic Activity for Amine Synthesis in Water
Yun, Xue-Jing,Ling, Chun,Deng, Wei,Liu, Zhen-Jiang,Yao, Zi-Jian
, p. 3830 - 3838 (2020/11/13)
Several types of β-ketoamino based N,O-coordinate half-sandwich ruthenium complexes have been synthesized in moderate to good yields. The stable ruthenium complexes displayed good and diverse catalytic efficiency in reductive amination between aldehydes and amines in aqueous solution. The method gave a facile route for one-pot synthesis of diverse complicated amines with a low catalyst loading by using cheap and less-toxic HCOOH or clean H2 as hydrogen source. Catalyst Ru1 showed the highest catalytic activity of 190 h-1 TOF value in the reductive amination reaction of benzaldehyde with aniline. The corresponding amine products were furnished in excellent yields under the standard catalysis system. The efficient and diverse catalytic activity, broad substance scope, mild conditions, and environmentally benign solvent made this system potentially applicable in industrial production. Ruthenium complexes were characterized using NMR, elemental analysis, and IR techniques to confirm their structure.