5129-86-2Relevant articles and documents
Bifunctional Ru-loaded Porous Organic Polymers with Pyridine Functionality: Recyclable Catalysts for N-Formylation of Amines with CO2 and H2
Zhang, Kai,Zong, Lingbo,Jia, Xiaofei
, p. 1335 - 1340 (2021/02/05)
A series of pyridine functionalized porous organic polymers (POPs-Py&PPh3) have been synthesized by polymerizing tris(4-vinylphenyl)phosphane and 4-vinylpyridine. The pyridine moieties in the copolymer materials contribute to CO2 adsorption and promote the subsequent conversion of CO2. The POP supported Ru catalyst (Ru/POP3-Py&PPh3) shows a high catalytic activity (TON up to 710) in the N-formylation of various primary and secondary amines with CO2/H2, affording the corresponding formamides in good yields (55–95%) under mild reaction conditions. The heterogeneous catalyst can be easily separated from the reaction system and reused for at least eight cycles in the N-formylation of morpholine. (Figure presented.).
Method for preparing formamide derivative by using catalyst-free transamination reaction
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Paragraph 0042; 0043, (2019/02/13)
The invention discloses a method for synthesizing a formamide derivative by using a low-reactive catalyst-free and solvent-free tertiary amide and aliphatic amine transamination reaction, wherein thehigh-yield formamide derivative is obtained by directly using N,N-dimethylformamide (DMF) as a formyl source. According to the present invention, the method has advantages of inexpensive and easily available raw materials, inexpensive and easily available acylating reagent, high reaction yield, one-step reaction, low cost, high reaction selectivity, simple operation and the like, and can overcomethe defects of high toxicity of the reaction reagent, requirement of different types of catalysts, high cost, more reaction steps, more by-products and the like in the prior art.
Methyl-Selective α-Oxygenation of Tertiary Amines to Formamides by Employing Copper/Moderately Hindered Nitroxyl Radical (DMN-AZADO or 1-Me-AZADO)
Nakai, Satoru,Yatabe, Takafumi,Suzuki, Kosuke,Sasano, Yusuke,Iwabuchi, Yoshiharu,Hasegawa, Jun-ya,Mizuno, Noritaka,Yamaguchi, Kazuya
supporting information, p. 16651 - 16659 (2019/11/11)
Methyl-selective α-oxygenation of tertiary amines is a highly attractive approach for synthesizing formamides while preserving the amine substrate skeletons. Therefore, the development of efficient catalysts that can advance regioselective α-oxygenation at the N-methyl positions using molecular oxygen (O2) as the terminal oxidant is an important subject. In this study, we successfully developed a highly regioselective and efficient aerobic methyl-selective α-oxygenation of tertiary amines by employing a Cu/nitroxyl radical catalyst system. The use of moderately hindered nitroxyl radicals, such as 1,5-dimethyl-9-azanoradamantane N-oxyl (DMN-AZADO) and 1-methyl-2-azaadamanane N-oxyl (1-Me-AZADO), was very important to promote the oxygenation effectively mainly because these N-oxyls have longer life-times than less hindered N-oxyls. Various types of tertiary N-methylamines were selectively converted to the corresponding formamides. A plausible reaction mechanism is also discussed on the basis of experimental evidence, together with DFT calculations. The high regioselectivity of this catalyst system stems from steric restriction of the amine-N-oxyl interactions.
