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1.
Org Biomol Chem ; 11(13): 2080-3, 2013 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-23435791

RESUMO

Appending a spirocyclopropane linkage to bicyclo[3.2.0]hept-2-ene is achieved by selective kinetic cyclopropanation of 6-methylenebicyclo[3.2.0]hept-2-ene. The resultant vinylcyclobutane undergoes [1,3] migration as the dominant thermal process. A minor cyclopropylcarbinyl (CPC) rearrangement product clearly implicates a diradical transition structure. The presence and absence of other potential thermal products have enabled us to construct a detailed mechanistic proposal to account for all viable dynamic processes.


Assuntos
Ciclobutanos/química , Ciclobutanos/síntese química , Ciclopropanos/química , Ciclopropanos/síntese química , Desenho de Fármacos , Radicais Livres/síntese química , Radicais Livres/química , Cinética , Estrutura Molecular , Especificidade por Substrato , Termodinâmica
2.
J Org Chem ; 77(7): 3468-74, 2012 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-22420624

RESUMO

cis,anti,cis-Tricyclo[7.4.0.0(2,8)]tridec-10-ene (13TCT) undergoes [1,3] sigmatropic rearrangements at 315 °C in the gas phase to the si product 1 and to the sr product 2 with si/sr = 2.1. The dominant thermal isomerization process, however, is epimerization at C8 to afford product 3. That stereomutation at C8 occurs 50% faster than the si and sr shifts combined.

3.
Orthop J Sports Med ; 10(11): 23259671221133105, 2022 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-36479459

RESUMO

Background: Patients with recurrent patellar dislocations with trochlear dysplasia are commonly treated surgically with a tibial tubercle osteotomy (TTO). Recovery and rehabilitation processes are often nonoperative out of concern for fixation failure or fracture. A more accelerated rehabilitation protocol allowing for early weightbearing and quadriceps strengthening may help to improve patient outcomes as long as complications are not increased. Purpose: To evaluate the safety and effectiveness of an accelerated weightbearing and early strengthening postoperative rehabilitation program for patients who undergo TTO. Study Design: Case series; Level of evidence, 4. Methods: Included were patients who underwent unilateral/staged bilateral TTO performed by a single surgeon between August 2013 and February 2018 with ≥6 months of follow-up. The surgical indication was primarily for patients with recurrent patellar instability. In all cases, a diagnostic arthroscopy was performed to evaluate the cartilage surfaces and document patellar tracking. The TTO was performed using a freehand technique and two 3.5-mm fully threaded screws for fixation. Patients underwent an accelerated postoperative rehabilitation program that allowed for weightbearing and lower extremity strengthening starting at 4 weeks. Objective and subjective outcome measures included any postoperative complications, knee range of motion, and patient-reported outcome scores (Kujala Anterior Knee Pain Scale [AKPS] and Knee injury and Osteoarthritis Outcome Score composite [(KOOS5]). Results: A total of 51 knees in 50 patients (38 female, 12 male) with a mean age of 31.24 ± 12.57 years were included in the final analysis. Compared with preoperative values, postoperative maximum knee flexion was significantly improved (117.67° ± 32.65° vs 131.12° ± 9.02°, respectively; P = .022). Postoperative complications included 6 patients with arthrofibrosis requiring manipulation under anesthesia, 4 with removal of symptomatic hardware, 1 tibial fracture (due to a fall), and 1 conversion to patellofemoral arthroplasty. The mean postoperative AKPS and KOOS5 scores were 72.98 ± 21.51 and 75.05 ± 16.02, respectively. Conclusion: Accelerated postoperative rehabilitation in TTO patients was an effective means of treatment with good subjective and objective outcomes and complication rates lower than traditional rehabilitation protocols.

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