7291-08-9Relevant articles and documents
Scalable and selective deuteration of (hetero)arenes
Bartling, Stephan,Beller, Matthias,Bourriquen, Florian,Brückner, Angelika,Junge, Kathrin,Kreyenschulte, Carsten,Lei, Aiwen,Li, Wu,Lund, Henrik,Rabeah, Jabor,Rockstroh, Nils,Surkus, Annette-Enrica,Yang, Dali
, (2022/01/19)
Isotope labelling, particularly deuteration, is an important tool for the development of new drugs, specifically for identification and quantification of metabolites. For this purpose, many efficient methodologies have been developed that allow for the small-scale synthesis of selectively deuterated compounds. Due to the development of deuterated compounds as active drug ingredients, there is a growing interest in scalable methods for deuteration. The development of methodologies for large-scale deuterium labelling in industrial settings requires technologies that are reliable, robust and scalable. Here we show that a nanostructured iron catalyst, prepared by combining cellulose with abundant iron salts, permits the selective deuteration of (hetero)arenes including anilines, phenols, indoles and other heterocycles, using inexpensive D2O under hydrogen pressure. This methodology represents an easily scalable deuteration (demonstrated by the synthesis of deuterium-containing products on the kilogram scale) and the air- and water-stable catalyst enables efficient labelling in a straightforward manner with high quality control. [Figure not available: see fulltext.].
Rhodium-catalyzed directed C–H functionalization of 2-arylindazoles with diazotized Meldrum's acid
Chen, Dongdong,Pan, Changduo,Yu, Jin-Tao,Yuan, Cheng
supporting information, (2021/08/10)
A rhodium-catalyzed alcohol-mediated ortho-functionalization of 2-aryl-2H-indazoles through sequential C-H activation and carbenoid insertion with diazotized Meldrum's acid was developed. Using the 2H-indazole as the directing group and alcohol as the alk
Rhodium-Catalyzed meta-Selective C?H Carboxylation Reaction of 1,1-Diarylethylenes via Hydrorhodation-Rhodium Migration
Caner, Joaquim,Iwasawa, Nobuharu,Saito, Takanobu,Toriumi, Naoyuki
, p. 23349 - 23356 (2021/09/18)
A meta-selective C?H carboxylation reaction of 1,1-diarylethylene derivatives with CO2 by using a rhodium catalyst with NaOiPr as a stoichiometric reductant has been achieved. Together with hydrogenation of the ethylene moiety, a carboxyl group was introduced to the meta-position of the aryl ring with high selectivity over the ortho-positions. Experimental and computational mechanistic studies indicate that this carboxylation reaction proceeds via hydrorhodation on the ethylene moiety, followed by 1,4-rhodium migration and successive 1,2-rhodium migration on the aryl ring. The use of a bulky phosphine ligand seems to be the key to this unusual aryl-to-aryl 1,2-rhodium shift.
Shifted Selectivity in Protonation Enables the Mild Deuteration of Arenes through Catalytic Amounts of Bronsted Acids in Deuterated Methanol
Fischer, Oliver,Hubert, Anja,Heinrich, Markus R.
, p. 11856 - 11866 (2020/10/23)
Taking advantage of the "differentiating effect"of the solvent methanol, deuterations of electron-rich aromatic systems can be carried out under mild acid catalysis and thus under far milder conditions than known so far. The exceptional functional group t
Substituted benzimidazole compound and composition with compound
-
Paragraph 0128-0133, (2019/03/31)
The invention provides a substituted benzimidazole compound and a composition with the compound. The substituted benzimidazole compound is a compound of formula (I) as shown in the specification, or apharmaceutically acceptable salt, prodrug, aquo-complex or solvent compound, polycrystalline type compound, stereisomer or isotope variant of the compound. The compound provided by the invention canbe adopted to treat and/or prevent related diseases caused by MEK (Methyl Ethyl Ketone), such as excessive proliferative diseases, pancreatitis, kidney illness, blastocyte cell transplantation and angiogenesis or angiopoiesis related diseases.
Chemo- And Regioselective Magnesium-Catalyzed ortho-Alkenylation of Anilines
Chatupheeraphat, Adisak,Rueping, Magnus,Magre, Marc
supporting information, p. 9153 - 9157 (2019/11/14)
A simple and efficient catalytic system for a chemo- and regioselective ortho-alkenylation of anilines is presented. The new magnesium-catalyzed reaction allows the use of a wide range of alkynes and anilines with different electronic and steric propertie
Cobalt-Catalyzed Regioselective Ortho C(sp2)-H Bond Nitration of Aromatics through Proton-Coupled Electron Transfer Assistance
Nageswar Rao, Desaboini,Rasheed, Sk.,Raina, Gaurav,Ahmed, Qazi Naveed,Jaladanki, Chaitanya Kumar,Bharatam, Prasad V.,Das, Parthasarathi
, p. 7234 - 7244 (2017/07/26)
A cobalt-catalyzed proton-coupled electron transfer (PCET) mediated regioselective ortho-specific nitration of aromatic C(sp2)-H bonds using chelation-assisted removable vicinal diamine directing groups was developed. The reaction proceeded under mild conditions in the presence of Co(OAc)2·4H2O as the catalyst with AgNO2 utilized as the nitro source as well as terminal oxidant in the presence of O2 as an external oxidant. No external base or additives were required for this process. Controlled experiments and mechanistic investigations with DFT calculations revealed that the reaction proceeds through a PCET promoted nitro functional group transfer pathway. Moreover, the produced compounds are valuable and pharmaceutically quite relevant.
ISOTOPOLOGUES OF ISOQUINOLINONE AND QUINAZOLINONE COMPOUNDS AND USES THEREOF AS PI3K KINASE INHIBITORS
-
Paragraph 00427, (2017/10/11)
Provided are isotopologues of isoquinolinone and quinazolinone compounds of formula (ΑΒ') that modulate PI3 kinase activity, processes for the preparation of the compounds, pharmaceutical compositions comprising the compounds, and methods of treatment of
Palladium/Silver Synergistic Catalysis in Direct Aerobic Carbonylation of C(sp2)H Bonds Using DMF as a Carbon Source: Synthesis of Pyrido-Fused Quinazolinones and Phenanthridinones
Nageswar Rao,Rasheed, Sk.,Das, Parthasarathi
supporting information, p. 3142 - 3145 (2016/07/13)
An unprecedented Pd/Ag synergistic catalysis in the direct carbonylation of C(sp2)-H bonds utilizing DMF as the carbon source under oxygen is described and demonstrated in the synthesis of pyrido-fused quinazolinone and phenanthridinone scaffolds. Control experiments indicated that the C of the carbonyl group is derived from the methyl group of DMF and O originates from oxygen as in the case of Ge's recent work. This transformation offers an alternative avenue for CO-free carbonylations.
Room-Temperature Cu(II)-Catalyzed Chemo- and Regioselective Ortho-Nitration of Arenes via C-H Functionalization
Sadhu, Pradeep,Alla, Santhosh Kumar,Punniyamurthy, Tharmalingam
, p. 8245 - 8253 (2015/09/01)
An efficient Cu-catalyzed chemo- and regioselective ortho-nitration of N,1-diaryl-5-aminotetrazoles and N,4-diaryl-3-amino-1,2,4-triazoles have been described with good functional group compatibility. The procedure features the use of operationally simple protocol utilizing the commercially available less toxic CuCl2·2H2O as catalyst and Fe(NO3)3·9H2O as nitration source at room temperature. Removal of the 5-aminotetrazole directing group has been demonstrated using base hydrolysis to afford substituted 2-nitroanilines.
