14925-09-8Relevant articles and documents
Photochemical study of tris(benzotriazol-1-yl)methane
Androsov, Dmitry A.,Neckers, Douglas C.
, p. 1148 - 1152 (2007)
(Chemical Equation Presented) Photodecomposition of tris(benzotrizol-1-yl) methane (1) in benzene gives [1-benzotryazol-1-yl-methylidene]-biphenyl-2- ylamine (2) resulting from the loss of the benzotriazolyl radical and nitrogen followed by addition of benzene. Elimination of the second benzotriazolyl radical from 2 provides the biphenyl-2-ylmethyleneamine radical, which affords phenantridine (3) after ring closure. In contrast, the photolysis of 1 in methanol gives a high yield of benzotriazole (4).
Novel orally active, dibenzazepinone-based γ-secretase inhibitors
Peters, Jens-Uwe,Galley, Guido,Jacobsen, Helmut,Czech, Christian,David-Pierson, Pascale,Kitas, Eric A.,Ozmen, Laurence
, p. 5918 - 5923 (2007)
Structural modifications of the γ-secretase inhibitor, LY411575, led to a malonamide analogue (S),(S)-1 with potent inhibitory activity in vitro, but disappointing activity in a mouse model of Alzheimer's disease. Identification and replacement of a metab
Metal-free directed C?H borylation of 2-(N-methylanilino)-5-fluoropyridines and 2-benzyl-5-fluoropyridines
Chen, Lu,Ji, Yafei,Ma, Tao,Pang, Binghan,Wang, Shuai,Wu, Gaorong,Xu, Xiaobo
supporting information, (2021/11/04)
A novel method for metal-free C?H borylation of 2-(N-methylanilino)-5-fluoropyridines and 2-benzyl-5-fluoropyridines has been reported. The 5-fluoropyridine directed borylation reaction exhibited high efficiency and site exclusivity. The useful protocol could be executed on a gram-scale easily and the borylated products showed good derivatization applications. Moreover, the practicality of the strategy was expanded by the fact that the directing group could be removed in an acceptable yield.
Transition-Metal-Free and Visible-Light-Mediated Desulfonylation and Dehalogenation Reactions: Hantzsch Ester Anion as Electron and Hydrogen Atom Donor
Heredia, Micaela D.,Guerra, Walter D.,Barolo, Silvia M.,Fornasier, Santiago J.,Rossi, Roberto A.,Budén, Mariá E.
, p. 13481 - 13494 (2020/12/15)
Novel approaches for N- and O-desulfonylation under room temperature (rt) and transition-metal-free conditions have been developed. The first methodology involves the transformation of a variety of N-sulfonyl heterocycles and phenyl benzenesulfonates to the corresponding desulfonylated products in good to excellent yields using only KOtBu in dimethyl sulfoxide (DMSO) at rt. Alternately, a visible light method has been used for deprotection of N-methyl-N-arylsulfonamides with Hantzsch ester (HE) anion serving as the visible-light-absorbing reagent and electron and hydrogen atom donor to promote the desulfonylation reaction. The HE anion can be easily prepared in situ by reaction of the corresponding HE with KOtBu in DMSO at rt. Both protocols were further explored in terms of synthetic scope as well as mechanistic aspects to rationalize key features of desulfonylation processes. Furthermore, the HE anion induces reductive dehalogenation reaction of aryl halides under visible light irradiation.
Aryl radical-induced desulfonylative: Ipso -substitution of diaryliodonium salts: An efficient route to sterically hindered biarylamines
Chen, Huangguan,Han, Jianwei,Wang, Limin
supporting information, p. 5697 - 5700 (2020/06/09)
By using vicinal aryl sulfonamide substituted diaryliodonium salts, a cascade of desulfonylation/aryl migration was promoted by triethylamine in the synthesis of sterically hindered biarylamines, which operated via a radical-induced reaction pathway. The products were readily converted into a variety of important synthons. Furthermore, coupling reactions of N-methyl biarylamine and 1,6-dibromopyrene provided a potentially attractive molecule in OLEDs.
Palladium-Catalyzed Methylation of Nitroarenes with Methanol
Wang, Lin,Neumann, Helfried,Beller, Matthias
supporting information, p. 5417 - 5421 (2019/04/04)
A procedure for the synthesis of N-methyl-arylamines directly from nitroarenes using methanol as green methylating agent was developed. The key to success is the use of a specific catalyst system consisting of palladium acetate and the ligand 1-[2,6-bis(isopropyl)phenyl]-2-[tert-butyl(2-pyridinyl)phosphino]-1H-Imidazole (L1). The generality of this protocol is demonstrated in the synthesis of more than 20 N-methyl-arylamines under comparably mild conditions. Combining this novel methodology with subsequent coupling processes using the same catalyst allows for efficient diversification of aromatic nitro compounds to a broad variety of amines including drug molecules.
Highly Selective N-Monomethylanilines Synthesis from Nitroarene and Formaldehyde via Kinetically Excluding of the Thermodynamically Favorable N,N-Dimethylation Reaction
Wang, Hongli,Yuan, Hangkong,Yang, Benqun,Dai, Xingchao,Xu, Shan,Shi, Feng
, p. 3943 - 3949 (2018/05/23)
The synthesis of N-monomethylamine remains a challenging topic because the N,N-dimethylation reaction is thermodynamically favorable. In this work, the kinetically controlled N-monomethylamine synthesis from nitroarene and paraformaldehyde/H2 is reported to have superhigh N-monomethylamine selectivity in the presence of a Pd/TiO2 catalyst. The superior selectivity should be attributed to the preferential adsorption of the primary amine over N-monomethylamine on the Pd/TiO2 surface, as elucidated by NH3/Me2NH-TPD, while the excellent catalytic activity could be associated with the good H2 activation ability and high amine adsorbing capacity of the catalyst, as elucidated by NH3-TPD and H2-TPR tests. Good results were obtained with a variety of nitroarenes containing methyl, methoxyl, hydroxyl, fluoride, trifluoromethyl, ester, and amide substituents as starting materials, and the potential synthetic utility of this protocol in pharmaceutical is illustrated by N-monomethylation of drug molecules, such as clinidipine, nimesulide, procaine, and methyl aminosalicylate.
Reductive C(sp2)-N elimination from isolated Pd(IV) amido aryl complexes prepared using H2O2 as oxidant
Abada, Elikplim,Zavalij, Peter Y.,Vedernikov, Andrei N.
supporting information, p. 643 - 646 (2017/05/16)
Di-2-pyridyl ketone (dpk)-supported amidoarylpallada(Il)cycles derived from various 2-(N-R-amino)biphenyls (R = H, Me, CF3CO, MeSOj, CF3SO2) react with hydrogen peroxide in MeOH, THF, MeCN or AcOH to form the corresponding C-N coupled products, N-R-substituted carbazoles, in 82-98% yield. For R = MeS02 and CF3SO2, the corresponding reaction intermediates, amidoaryl Pd(IV) complexes were isolated and characterized by single crystal X-ray diffraction and/or NMR spectroscopy. For the first time, the C(sp2)-N reductive elimination from isolated amidoaryl Pd(lV) complexes has been studied in detail.
Mono-N-methylation of anilines with methanol catalyzed by a manganese pincer-complex
Bruneau-Voisine, Antoine,Wang, Ding,Dorcet, Vincent,Roisnel, Thierry,Darcel, Christophe,Sortais, Jean-Baptiste
, p. 57 - 62 (2017/02/13)
The selective mono-N-methylation of anilines derivatives was achieved under mild conditions using inexpensive methanol as C1 source. Under hydrogen borrowing conditions, using a tridentate PN3P manganese pre-catalyst (5?mol%), a catalytic amount of base (20?mol%), for 24?h at 120?°C, a large variety of anilines derivatives was methylated in good to excellent yield. Mechanistic investigations allowed us to isolate and characterize by X-ray diffraction studies a de-aromatized manganese intermediate.
SILYLATION OF AROMATIC HETEROCYCLES BY EARTH ABUNDANT TRANSITION-METAL-FREE CATALYSTS
-
Paragraph 0232, (2016/04/26)
The present invention describes chemical systems and methods for silylating aromatic organic substrates, said system or method comprising or consisting essentially of a mixture of (a) at least one organosilane and (b) at least one strong base, the definition of strong base now also including hydroxide, especially KOH, said system being preferably, but not necessarily substantially free of a transition-metal compound, and said methods comprising contacting a quantity of the organic substrate with a mixture of (a) at least one organosilane and (b) at least one strong base, under conditions sufficient to silylate the aromatic substrate; wherein said system is substantially free of a transition-metal compound.
