60433-00-3Relevant academic research and scientific papers
Enantioselective Intermolecular C-H Amination Directed by a Chiral Cation
Fanourakis, Alexander,Paterson, Kieran J.,Phipps, Robert J.,Williams, Benjamin D.
supporting information, p. 10070 - 10076 (2021/07/21)
The enantioselective amination of C(sp3)-H bonds is a powerful synthetic transformation yet highly challenging to achieve in an intermolecular sense. We have developed a family of anionic variants of the best-in-class catalyst for Rh-catalyzed C-H amination, Rh2(esp)2, with which we have associated chiral cations derived from quaternized cinchona alkaloids. These ion-paired catalysts enable high levels of enantioselectivity to be achieved in the benzylic C-H amination of substrates bearing pendant hydroxyl groups. Additionally, the quinoline of the chiral cation appears to engage in axial ligation to the rhodium complex, providing improved yields of product versus Rh2(esp)2 and highlighting the dual role that the cation is playing. These results underline the potential of using chiral cations to control enantioselectivity in challenging transition-metal-catalyzed transformations.
Alkoxycarbonylation of olefins with carbon dioxide by a reusable heterobimetallic ruthenium-cobalt catalytic system
Zhang, Xuehua,Shen, Chaoren,Xia, Chungu,Tian, Xinxin,He, Lin
supporting information, p. 5533 - 5539 (2019/01/03)
The heterobimetallic ruthenium-cobalt catalytic system exhibited good catalytic performance and reusability in the reductive alkoxycarbonylation of olefins with carbon dioxide. Compared to the previous system only consisting of ruthenium catalyst, the binary catalyst system effectively reduced the usage of noble metal and ionic liquid additives. The respective contribution of ruthenium and cobalt catalysts in this multiple-step catalytic process was investigated by a series of condition-controlled experiments. The evolution of the ruthenium catalyst and the occurrence of alkene hydrogenation during the reaction was explained by theortical calculations.
Palladium-catalyzed selective generation of CO from formic acid for carbonylation of alkenes
Sang, Rui,Kucmierczyk, Peter,Dong, Kaiwu,Franke, Robert,Neumann, Helfried,Jackstell, Ralf,Beller, Matthias
supporting information, p. 5217 - 5223 (2018/04/24)
A general and selective palladium-catalyzed alkoxycarbonylation of all kinds of alkenes with formic acid (HCOOH, FA) is described. Terminal, di-, tri-, and tetra-substituted including functionalized olefins are converted into linear esters with high yields and regioselectivity. Key-to-success is the use of specific palladium catalysts containing ligands with built-in base, e.g., L5. Comparison experiments demonstrate that the active catalyst system not only facilitates isomerization and carbonylation of alkenes but also promotes the selective decomposition of HCOOH to CO under mild conditions.
Palladium-Catalyzed Carbonylation of sec- and tert-Alcohols
Dong, Kaiwu,Sang, Rui,Liu, Jie,Razzaq, Rauf,Franke, Robert,Jackstell, Ralf,Beller, Matthias
supporting information, p. 6203 - 6207 (2017/05/22)
A general palladium-catalyzed synthesis of linear esters directly from sec- and tert-alcohols is described. Compared to the classic Koch–Haaf reaction, which leads to branched products, this new transformation gives the corresponding linear esters in high yields and selectivity. Key for this protocol is the use of an advanced palladium catalyst system with L2 (pytbpx) as the ligand. A variety of aliphatic and benzylic alcohols can be directly used and the catalyst efficiency for the benchmark reaction is outstanding (turnover number up to 89 000).
APOPTOSIS-INDUCING AGENTS FOR THE TREATMENT OF CANCER AND IMMUNE AND AUTOIMMUNE DISEASES
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Paragraph 1676, (2013/04/24)
Disclosed are compounds which inhibit the activity of anti-apoptotic Bc1-xL proteins, compositions containing the compounds and methods of treating diseases during which is expressed anti-apoptotic Bc1-xL protein.
SIGMA RECEPTOR BINDER CONTAINING INDANONE DERIVATIVE
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Page/Page column 18, (2008/06/13)
The present invention provides an indanone derivative and an excellent sigma receptor binding agent comprising an indanone derivative. More specifically, it provides a sigma receptor binding agent comprising an indanone derivative represented by the following formula, a pharmacologically acceptable salt thereof or a hydrate of them. In the formula (I), R1, R2, R3 and R4 are the same as or different from each other and each represents hydrogen atom, a halogen atom, hydroxyl group, nitrile group, a C1-6 alkyl group which may be substituted, a cycloalkyl group having three to eight carbon atoms which may be substituted, a C1-6 alkoxy group which may be substituted, a cycloalkoxy group having three to eight carbon atoms which may be substituted, an acyl group having one to six carbon atoms which may be substituted, a C1-6 alkoxycarbonyl group which may be substituted, a C1-6 alkylaminocarbonyloxy group which may be substituted, a di(C1-6 alkyl)aminocarbonyloxy group which may be substituted, nitro group, an amino group which may be substituted, an amido group which may be substituted, mercapto group or a thio-C1-6 alkoxy group which may be substituted, and further R1 with R2, R2 with R3, or R3 with R4 may together form an aliphatic ring, an aromatic ring, a heterocyclic ring or an alkylenedioxy ring; the partial structure: represents a group represented by >CH-CH2-, >C=CH- or >C(-R7)-CH2-; m represents an integer of 0 or 1 to 5; and R5 represents hydrogen atom, a C1-6 alkyl group which may be substituted, a C2-6 alkenyl group which may be substituted, a C2-6 alkynyl group which may be substituted, a cycloalkyl group having three to eight carbon atoms which may be substituted, a 2,2-(alkylenedioxy)ethyl group or a group represented by the formula: (wherein the ring C represents benzene ring, an aliphatic ring or a heterocyclic ring; R6s are the same as or different from each other and each represents hydrogen atom, a halogen atom, hydroxyl group, nitrile group, a C1-6 alkyl group which may be substituted, a C2-6 alkenyl group which may be substituted, a C2-6 alkynyl group which may be substituted, a cycloalkyl group having three to eight carbon atoms which may be substituted, a C1-6 alkoxy group which may be substituted, a C1-6 alkoxyalkoxy group which may be substituted, an aryloxy group which may be substituted or an aralkyloxy group which may be substituted, and further two of R6s may together form an aliphatic ring, an aromatic ring, a heterocyclic ring or an alkylenedioxy ring; R7 represents a halogen atom, hydroxyl group, a C1-6 alkyl group which may be substituted, a C1-6 alkoxy group, nitrile group, a halogeno-C1-6 alkyl group, a hydroxyl-C1-6 alkyl group, a cyano-C1-6 alkyl group, an amino-C1-6 alkyl group, nitro group, azide group, an amino group which may be substituted, a carbamoyl group which may be substituted, a carboxyl group which may be substituted, mercapto group or a thio-C1-6 alkoxy group; and n represents an integer of 1 to 5), provided that 1-benzyl-4-[(5,6-dimethoxy-1-indanon)-2-yl]methylpiperidine, a pharmacologically acceptable salt thereof or a hydrate of them are excluded.
Indirect electrochemical oxidation of cyclic ketones: Influence of ring size, mediator and supporting electrolyte on the result of the reaction
Barba, Fructuoso,Elinson, Michail N.,Escudero, Jose,Feducovich, Sergey K.
, p. 4427 - 4436 (2007/10/03)
The result of the indirect electrochemical oxidation of cyclic ketones in methanol in an undivided cell in the presence of sodium halides depends on the ring size of ketone and the type of mediator. Selectivity of the reaction in some cases and current efficiency are increased by addition of supporting electrolyte - sodium hydroxide. Formation of cyclic 2,2-dimethoxycycloalkanols and the electrochemically induced Favorskii rearrangement with the formation of methyl cycloalkencarboxylates containing in the ring one carbon atom less than starting ketone are the main ways of the indirect electrochemical oxidation of cyclic ketones.
Indirect electrochemical oxidation of cyclic ketones: Strong influence of ring size on the result of the reaction
Barba, Fructuoso,Elinson, Michail N.,Escudero, Jose,Feducovich, Sergey K.
, p. 5759 - 5762 (2007/10/03)
The result of the indirect electrochemical oxidation of cyclic ketones in methanol in the undivided cell in the presence of sodium iodide depends on the ring size. Cyclopentanone affords 2,2-dimethoxycyclopentanone. While cyclohexanone gives rise 2,2-dimethoxycyclo-hexanol, and cyclic ketones with higher ring size undergo new type of the electrochemically induced Favorskii rearrangement with the formation of methyl cycloalkencarboxylates containing in the ring on the one carbon atom less than starting ketone. So the simple electrocatalytic system can distinguish the ring size of cyclic ketones.
OXYCHLORINATION OF ALKENES BY CHLOROCHROMATE REAGENTS: A FACILE PREPARATION OF α-CHLOROKETONES, AND COMPETITION BY SUBSTITUENT-DIRECTED OXIDATION.
Guerrero, Angel F.,Kim, Ho-jin,Schlecht, Matthew F.
, p. 6707 - 6710 (2007/10/02)
Cyanopyridinium chlorochromate effects a facile preparation of α-chloroketones from simple alkenes, cycloocta-1,5-diene and cyclododeca-1,5,9-triene; 1-methylcaclooct-4-en-1-ol undergoes oxidative cyclization.
