Intermolecular C-H silylations of arenes and heteroarenes with mono-, bis-, and tris(trimethylsiloxy)hydrosilanes: control of silane redistribution under operationally diverse approaches.

Efficient catalytic protocols for C-H silylations of arenes and heteroarenes with sterically and electronically different hydrosiloxysilanes are disclosed. The silylations are catalyzed by a well-defined Rh-complex (1 mol%), derived from [Rh(1,5-hexadiene)Cl]2 and a bulky BINAP type ligand. This catalyst not only promotes C-Si bond formation affording the desired products in up to 95% isolated yield, but also can suppress the silane redistribution side reactions of HSiMe2(OTMS). The protocol can also be applied for the C-H silylations of more reactive HSiMe(OTMS)2 with a much lower catalyst loading (0.25 mol%) and even with sterically demanding HSi(OTMS)3. The steric bulk of the arene substituent and hydrosiloxysilane is a major factor in determining the regioselectivity and electronic effect as secondary. The current method can be performed under operationally diverse conditions: with/without a hydrogen scavenger or solvent.

Evaluating the Evolving Morbidity of Omentoplasty for Perforated Peptic Ulcer Disease.

Mortality for perforated peptic ulcer (PPU) surgery ranges from 2-22% with morbidity ranging from 15-45%. Traditionally, these had been repaired with vagotomy and antrectomy or pyloroplasty with smaller perforations repaired with an omentoplasty. Laparoscopic repair has become increasingly prevalent and demonstrated to have shorter length of stay (LOS) and fewer complications. We are evaluating the surgical repair of PPU with omentoplasty to determine trends of utilization and surgical outcomes. We conducted a 13-year (2005-2017) retrospective review, utilizing the National Surgical Quality Improvement Program database. A total of 6873 patients had open or laparoscopic repair of a PPU, with 2285 patients identified as utilizing omentoplasty. Five hundred eighty-eight omentoplasty patients were further identified as having a laparoscopic technique. We compared patient demographics, comorbidities, and perioperative morbidity and mortality for surgical patients between 2005-2011 and 2012-2017. We trended the perioperative outcomes across the study intervals. Parametric and nonparametric tests were used to evaluate outcomes. Between 2005 and between 2017, laparoscopic surgical repair with omentoplasty has increased from 3.8% to 34.6%. Overall mortality for open operations declined during this interval (12.7%-9.3%) while it remained unchanged for laparoscopic operations (4.6%-4.2%), there was not a significant difference between the laparoscopic and open 30-day mortality. Both open surgery and laparoscopic surgery are being used on an increasingly healthy cohort (increased functional status decreased predicted perioperative morbidity). Relative to the 2005-2011, the laparoscopic surgery 2012-2017 cohort had increases in both serious and overall morbidity, although this was not statistically significant. Compared to the 2005-2011, the 2012-2017 open surgery cohort had increasing serious morbidity (OR 2.03) and overall morbidity (OR 1.91). There was a trend of decreasing LOS and increased return to the operating room for patients with laparoscopic surgery. Laparoscopic Graham patch repair of peptic ulcers significantly increased, although open repair still constitutes the majority of the cases. Despite Graham patch repair being utilized on a healthier patient population, morbidity and mortality for laparoscopic repair have remained unchanged. Postoperative morbidity and mortality for open surgery have increased. This indicates that laparoscopic repair is more commonly utilized for low- or medium risk patients, leaving an increasingly sick patient population selected to open repair.

The Bethesda Classification for Thyroid Fine Needle Aspiration: A Predictor or an Alarmist?

Thyroid malignancies comprise only 2 per cent of all cancers. Yet the incidence of thyroid cancers has been increasing faster than other malignancies, likely due to increased screening and surveillance of thyroid nodules. The Bethesda system represents the preferred method of evaluating thyroid nodules for malignancy using fine needle aspiration (FNA). Many thyroidectomies are performed for small, asymptomatic nodules found on ultrasound. These small papillary cancers (<0.5 cm) are termed microcarcinomas and represent a more indolent natural history causing some to name them "occult papillary tumors." The objective is to assess the relationship between the Bethesda classification and pathologic stage of thyroid cancer with attention to T1a lesions. A single institution, retrospective study of thyroidectomy patients who had a preoperative FNA and a final pathology of thyroid malignancy were performed. The distribution of stage relative to Bethesda classification was significantly different than expected (P = 0.00382). The low risk Bethesda II, (odds ratio;OR 9.15, 2.7931-29.97, P = 0.0003) and the intermediate group, Bethesda III, (OR 3.48, 1.4436-8.4124, P = 0.0055) had a statistically significant higher incidence of T1a. The Bethesda classification for thyroid FNA falls short in the accuracy of intermediate stage malignancies. Patients whose FNA were Bethesda II or III had a higher likelihood of indolent T1a disease.