Investigation on the Synthesis, Application and Structural Features of Heteroaryl 1,2-Diketones

A set of unsymmetrical heteroaryl 1,2-diketones were synthesized by a heteroarylation/oxidation sequence with up to 65% isolated yields. Palladium catalyst XPhos Pd G4 and SeO2 were the key reagents used in this methodology, and microwave irradiation was utilized to facilitate an efficient and ecofriendly process. The application of heteroaryl 1,2-diketones is demonstrated through the synthesis of an unsymmetrical 2-phenyl-3-(pyridin-3-yl)quinoxaline (5a) from 1-phenyl-2-(pyridin-3-yl)ethane-1,2-dione (4a). The lowest energy conformations of 4a and 5a were located using Density Functional Theory (DFT) at the M06-2X/def2-TZVP level of theory. Two lowest energy conformations of 4a differ with respect to the position of the N atom in the pyridyl ring and 0.27 kcal/mol energy difference between them corresponds to 60.4 and 39.6% at 50 °C in toluene. Four lowest energy conformations for 5a have the energy differences of 0.01, 0.03 and 0.07 kcal/mol that corresponds to 26.0, 25.7, 24.9 and 23.4%, respectively. A comparison of 4a and 5a to the less hindered analogs (oxalyl chloride and oxalic acid) is used to investigate the structural features and bonding using Natural Bond Orbital (NBO) analysis

Investigation on the Synthesis, Application and Structural Features of Heteroaryl 1,2-Diketones

A set of unsymmetrical heteroaryl 1,2-diketones were synthesized by a heteroarylation/oxidation sequence with up to 65% isolated yields. Palladium catalyst XPhos Pd G4 and SeO2 were the key reagents used in this methodology, and microwave irradiation was utilized to facilitate an efficient and ecofriendly process. The application of heteroaryl 1,2-diketones is demonstrated through the synthesis of an unsymmetrical 2-phenyl-3-(pyridin-3-yl)quinoxaline (5a) from 1-phenyl-2-(pyridin-3-yl)ethane-1,2-dione (4a). The lowest energy conformations of 4a and 5a were located using Density Functional Theory (DFT) at the M06-2X/def2-TZVP level of theory. Two lowest energy conformations of 4a differ with respect to the position of the N atom in the pyridyl ring and 0.27 kcal/mol energy difference between them corresponds to 60.4 and 39.6% at 50 °C in toluene. Four lowest energy conformations for 5a have the energy differences of 0.01, 0.03 and 0.07 kcal/mol that corresponds to 26.0, 25.7, 24.9 and 23.4%, respectively. A comparison of 4a and 5a to the less hindered analogs (oxalyl chloride and oxalic acid) is used to investigate the structural features and bonding using Natural Bond Orbital (NBO) analysis

Medial patellar luxation repair in a seven month-old cat

A seven month-old female spayed Manx cat presented to the orthopedic service at CUHA in fall 2011 for assessment of previously diagnosed bilaterally luxating patellae. The patient first began having difficulty walking at five months of age and had undergone initial evaluation at Community Practice Services (CPS). At that time she was diagnosed with bilaterally luxating patellae through an orthopedic consultation. She was sent home with oral buprenorphine to address associated pain. The owner did not feel the buprenorphine was effective and returned to the orthopedic service for further work-up and to explore more definitive treatment. The main presenting complaint was episodes occurring about two times a day where the cat would acutely straighten one or both hind limbs as if painful. These episodes would often be associated with a sharp movement. After a period of rigid hind limb posture during which it appeared to the owner as if the cat was unable to bend her hind legs, the patient would work her way out of the posture and regain use of her hind limbs. The patient also experienced periods of hind limb weakness and would sometimes lie down abruptly during weight-bearing activity as if she were acutely painful. At presentation the patient was up to date on her annual preventive vaccines and had tested FeLV/FIV negative. She had no prior history of medical problems, though the owner noted she was approximately half the size of a littermate also owned by the family and she had been born with no tail