42864-21-1Relevant academic research and scientific papers
Catalytic Decarboxylative C?N Formation to Generate Alkyl, Alkenyl, and Aryl Amines
Zhang, Yipin,Ge, Xia,Lu, Hongjian,Li, Guigen
supporting information, p. 1845 - 1852 (2020/12/01)
Transition-metal-catalyzed sp2 C?N bond formation is a reliable method for the synthesis of aryl amines. Catalytic sp3 C?N formation reactions have been reported occasionally, and methods that can realize both sp2 and sp3 C?N formation are relatively unexplored. Herein, we address this challenge with a method of catalytic decarboxylative C?N formation that proceeds through a cascade carboxylic acid activation, acyl azide formation, Curtius rearrangement and nucleophilic addition reaction. The reaction uses naturally abundant organic carboxylic acids as carbon sources, readily prepared azidoformates as the nitrogen sources, and 4-dimethylaminopyridine (DMAP) and Cu(OAc)2 as catalysts with as low as 0.1 mol % loading, providing protected alkyl, alkenyl and aryl amines in high yields with gaseous N2 and CO2 as the only byproducts. Examples are demonstrated of the late-stage functionalization of natural products and drug molecules, stereospecific synthesis of useful α-chiral alkyl amines, and rapid construction of different ureas and primary amines.
Multi-functional aromatic amine compound as well as preparation method and application thereof
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Paragraph 0128-0133, (2021/08/14)
The invention belongs to the technical field of synthesis of aromatic amine compounds, and particularly relates to a multi-functional aromatic amine compound as well as a preparation method and application thereof. The invention provides a multi-functional aromatic amine compound and also provides a preparation method of the multi-functional aromatic amine compound. The amination reaction of aromatic carboxylic acid is catalyzed by DMAP at a relatively low temperature under the condition of no transition metal, and the method can be used for synthesizing a series of multi-functional aromatic amine compounds. The preparation method has not been reported in literature at present. The invention also provides a derivative product of arylamine and a preparation method thereof, and an application of the multi-functional aromatic amine compound in later modification of active molecules. The compound can be used for construction of optical active urea compounds and some important active molecules, and has a development prospect in synthesis of active drugs and natural products.
Acylamino-Directed Specific Sequential Difunctionalizations of Anilides via Metal-Free Relay Reactions for p-Oxygen and o-Nitrogen Incorporation
Wan, Yameng,Zhang, Zhiguo,Ma, Nana,Bi, Jingjing,Zhang, Guisheng
, p. 780 - 791 (2019/01/24)
Novel acylamino-directed relay disubstitutions realize the sequential difunctionalizations of anilides (1) under mild and metal-free conditions for the first time. This [bis(trifluoroacetoxy)iodo]benzene (PIFA) and BF3·Et2O promoted straightforward reaction produces a series of p-acetoxyl- or p-alkoxyl-o-nitro-N-arylamides (2), which are key scaffolds of various drugs, functional materials, and bioactive molecules. The flexibility with respect to the functional groups in these products affords this novel protocol excellent versatility for synthetic applications.
A synthetic approach to N -aryl carbamates via copper-catalyzed Chan-Lam coupling at room temperature
Moon, Soo-Yeon,Kim, U. Bin,Sung, Dan-Bi,Kim, Won-Suk
, p. 1856 - 1865 (2015/02/19)
A mild and efficient synthesis of N-arylcarbamates was achieved by reacting azidoformates with boronic acids in the presence of 10 mol % of copper chloride catalyst. The reaction proceeds readily in an open flask at room temperature without additional base, ligand, or additive. Rapid access to urea analogues via a two-step one-pot procedure is enabled by reacting N-arylcarbamates with aluminum-amine complexes. In addition, among several boronic acid derivatives prepared, dimethylphenyl boronate was found to react rapidly in its reaction with benzyl azidoformate, invoking in situ generation of this species in the catalytic cycle.
Copper-catalyzed C2-H amidation of unactivated arenes by N-tosyloxycarbamates
John, Alex,Byun, Jeena,Nicholas, Kenneth M.
supporting information, p. 10965 - 10967 (2013/11/19)
(Neocuproine)Cu PF6 catalyzes the C-H amidation of unactivated arenes by N-tosyloxytrichloroethylcarbamates. Alkyl benzenes are selectively converted to aromatic amines and substituted arenes display variable regioselectivity. The Royal Society of Chemistry 2013.
Platinum on carbon-catalyzed precise reduction control of trichloromethyl to Geminal-dichloromethyl groups
Imanishi, Takahiro,Fujiwara, Yuta,Sawama, Yoshinari,Monguchi, Yasunari,Sajiki, Hironao
supporting information; experimental part, p. 771 - 776 (2012/06/30)
Geminal-dichloromethyl derivatives could be efficiently synthesized by the highly chemoselective platinum on carbon-catalyzed mono-dechlorination of trichloromethyl substrates in dimethylacetamide (DMA) as a specific solvent at 25 °C under a hydrogen atmosphere. Copyright
Convenient method for the preparation of carbamates, carbonates, and thiocarbonates
Shimizu, Mamoru,Sodeoka, Mikiko
, p. 5231 - 5234 (2008/09/17)
(Chemical Equation Presented) A convenient, rapid, and efficient method for the preparation of carbamates from amines with 1-alkoxycarbonyl-3-nitro-1,2,4- triazole transfer reagents is reported. Reactions of newly synthesized stable crystalline reagents with alkyl amines were completed in a few minutes without any additional base, and highly pure carbamates were obtained without chromatographic purification. These highly active reagents are also useful for the selective protection of nucleobases and preparation of carbonates and thiocarbonates.
A new practical method for the synthesis of unsymmetrical ureas via high-pressure-promoted condensation of 2,2,2-trichloroethyl carbamates (Troc-carbamates) with amines
Azad, Saleha,Kumamoto, Koji,Uegaki, Kaoru,Ichikawa, Yoshiyasu,Kotsuki, Hiyoshizo
, p. 587 - 590 (2007/10/03)
A new practical method for the synthesis of unsymmetrical ureas was achieved by condensation between 2,2,2-trichloroethyl carbamates (Troc-carbamates) and primary or secondary amines under high-pressure conditions.
