66735-01-1Relevant academic research and scientific papers
Palladium-Catalyzed C(sp3)-H Nitrooxylation with tert-Butyl Nitrite and Molecular Oxygen
Han, Ye-Qiang,Li, Bo,Shi, Bing-Feng,Yang, Xu
supporting information, p. 9719 - 9723 (2020/12/21)
Herein, we report a Pd(II)-catalyzed nitrooxylation of unactivated methyl C(sp3)-H bonds using commercial available and easily manageable tert-butyl nitrite as the precursor of ONO2 radical under aerobic conditions. Environmentally benign molecular oxygen is used to initiate the generation of active radical reactant; it is also used as the terminal oxidant. A broad range of nitrooxylated aliphatic carboxamides were prepared in moderate to good yields under mild conditions.
Cobalt-Catalyzed Asymmetric Hydrogenation of α,β-Unsaturated Carboxylic Acids by Homolytic H2 Cleavage
Chirik, Paul J.,Shevlin, Michael,Zhong, Hongyu
supporting information, (2020/03/13)
The asymmetric hydrogenation of α,β-unsaturated carboxylic acids using readily prepared bis(phosphine) cobalt(0) 1,5-cyclooctadiene precatalysts is described. Di-, tri-, and tetra-substituted acrylic acid derivatives with various substitution patterns as well as dehydro-α-amino acid derivatives were hydrogenated with high yields and enantioselectivities, affording chiral carboxylic acids including Naproxen, (S)-Flurbiprofen, and a d-DOPA precursor. Turnover numbers of up to 200 were routinely obtained. Compatibility with common organic functional groups was observed with the reduced cobalt(0) precatalysts, and protic solvents such as methanol and isopropanol were identified as optimal. A series of bis(phosphine) cobalt(II) bis(pivalate) complexes, which bear structural similarity to state-of-the-art ruthenium(II) catalysts, were synthesized, characterized, and proved catalytically competent. X-band EPR experiments revealed bis(phosphine)cobalt(II) bis(carboxylate)s were generated in catalytic reactions and were identified as catalyst resting states. Isolation and characterization of a cobalt(II)-substrate complex from a stoichiometric reaction suggests that alkene insertion into the cobalt hydride occurred in the presence of free carboxylic acid, producing the same alkane enantiomer as that from the catalytic reaction. Deuterium labeling studies established homolytic H2 (or D2) activation by Co(0) and cis addition of H2 (or D2) across alkene double bonds, reminiscent of rhodium(I) catalysts but distinct from ruthenium(II) and nickel(II) carboxylates that operate by heterolytic H2 cleavage pathways.
Heterocyclic compounds
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, (2008/06/13)
The invention concerns pharmaceutically useful compounds of the formula I, in which A1, A2, A3, A4, B1, m, Ar, W, X, Y, Z and R1 have any of the meanings defined herein, and their pharmaceutically acceptable salts, and pharmaceutical compositions containing them. The novel compounds possess endothelin receptor antagonist activity and are useful, for example, in the treatment of diseases or medical conditions in which elevated or abnormal levels of endothelin play a significant causative role. The invention further concerns processes for the manufacture of the novel compounds and the use of the compounds in medical treatment.
