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To investigate the association between Barthel Index (BI), which measures level of patients independence during daily living activities (ADL), and perioperative outcomes in a large cohort of consecutive bladder cancer (BCa) patients, who underwent radical cystectomy (RC) at a tertiary referral center.We retrospectively evaluated data from clinically nonmetastatic BCa patients treated with RC between 2015 and 2022. For each patient, BI was assessed preoperatively. According to BI score, patients were divided into three groups: ≤60 (total/severe dependency) vs. 65-90 (moderate dependency) vs. 95-100 (slight dependency/independency). Regression analyses tested the association between BI score and major postoperative complications (Clavien-Dindo2), length of in-hospital stay (LOHS), 90-days readmission, and total costs.Overall, 288 patients were included. According to BI score, the patient cohort was distributed as follows: 4% (n = 11) BI ≤60 vs. 15% (n = 42) BI 65-90 vs. 81% (n = 235) BI 95-100. Patients with BI ≤60 had more frequent ureterocutaneostomy performed, shorter operative time, higher rates of postoperative complications, longer LOHS, higher rates of readmission, and were associated with higher total costs, compared to patients with BI 65-90 and 95-100. In multivariable regression models, BI ≤60 remained an independent predictor of increased risk of major postoperative complications (odds ratio: 6.62, p = 0.006), longer LOHS (rate ratio: 1.25, p 0.001), and higher costs (β: 2.617, p = 0.038).Total/severe dependency in ADL assessed by BI was associated with higher rates of major postoperative complications, longer hospitalization, and higher costs in BCa patients treated with RC. BI assessment should be considered during patients selection process and counseling before surgery.

The numbers needed to image to identify pelvic lymph node and/or distant metastases in newly diagnosed prostate cancer (PCa) patients according to risk level are unknown.Relying on Surveillance, Epidemiology, and End Results (2010-2016), we tabulated rates and proportions of patients with (a) lymph node or (b) distant metastases according to National Comprehensive Cancer Network (NCCN) risk level and calculated the number needed to image (NNI) for both endpoints. Multivariable logistic regression analyses were performed.Of 145,939 newly diagnosed PCa patients assessable for analyses of pelvic lymph node metastases (cN1), 4559 (3.1%) harbored cN1 stage: 13 (0.02%), 18 (0.08%), 63 (0.3%), 512 (2.8%), and 3954 (14.9%) in low, intermediate favorable, intermediate unfavorable, high, and very high-risk levels. These resulted in NNI of 4619, 1182, 319, 35, and 7, respectively. Of 181,109 newly diagnosed PCa patients assessable for analyses of distant metastases (M1Our observations perfectly validated the NCCN recommendations for imaging in newly diagnosed high and very high-risk PCa patients. However, in unfavorable intermediate-risk PCa patients, in whom bone and soft tissue imaging is recommended, the NNI might be somewhat elevated to support routine imaging in clinical practice.

Background To evaluate the role of computed tomography (CT) and positron emission tomography (PET)/CT in patients with thymic cancer and thymoma at initial staging. Methods We retrospectively reviewed CT and PET/CT scans of 26 patients with a thymic cancer (n = 9) or thymoma (n = 17). Chest CT findings documented were qualitative and quantitative. Both qualitative and semiquantitative data were recovered by PET/CT. The comparisons among histological entities, outcome, and qualitative data from CT and PET/CT were made by non-parametric analysis. Results PET/CT resulted positive in 15/17 patients with thymoma. CT was available in 5/9 (56%) patients with thymic cancer and in 3/17 with thymoma. All quantitative CT parameters were significantly higher in patients with thymic cancer than thymoma (maximum axial diameter: 45 vs. 20 mm, maximum longitudinal diameter: 69 vs. 21 mm and volume: 77.91 vs. 4.52 mL; all P < 0.05). Conversely, only metabolic tumor volume (MTV) and total lesion glycolysis were significantly different in patients with thymic cancer than thymoma (126.53 vs. 6.03 cm3 and 246.05 vs. 20.32, respectively; both P < 0.05). After a median follow-up time of 17.45 months, four recurrences of disease occurred: three in patients with thymic cancer and one with a type B2 thymoma. CT volume in patients with recurrent disease was 102.19 mL versus a median value of 62.5 mL in six disease-free patients. MTV was higher in the recurrent than disease-free patient subset (143.3 vs. 81.13 cm3), although not statistically significant (P = 0.075). Conclusion Our preliminary results demonstrated that both morphological and metabolic volume could be useful from a diagnostic and prognostic point of view in thymic cancer and thymoma patients. A large multi-center clinical trial experience for confirming the findings of this study seems mandatory.

α-Alkyl-α-aryl (trimethyltin) nitriles react spontaneously with aldehydes and ketones in THF/toluene to give β-hydroxy nitriles with satisfactory to good yields and diastereoselectivity. No extra catalyst is required in this aldol-like reaction. A possible trimethyltin-substituted ketene imine intermediate is invoked as reactive species. DFT calculations offer good support for this hypothesis.

Preparation of piperidine-2-one scaffolds by the hetero-Diels-Alder (HAD) reaction, assisted by microwaves, is described. The versatility of this new approach has been demonstrated by the synthesis of racemic (+/-)-2-phenylpiperidine. Theoretical calculations have allowed us to clarify the factors that govern ring closure to form four-membered rings, arising from a Staudinger-type electrocyclization, and/or six-membered rings through a classical [4+2] HAD cyclization. This competition may be lowered by increasing the electronic demand of the dienophile, as anticipated by the computational studies.

Aim: To assess the potential role of 18F-Fluorodeoxiglucose (FDG) Positron Emission Tomography (PET)/Computed Tomography (CT) in characterizing indeterminate lung nodules detected at CT scan in patients previously treated for a breast cancer (BC). Materials and Methods: Twenty-nine consecutive BC patients (28 females, mean age 65 ± 12 years) with evidence of indeterminate lung nodules at contrast-enhanced CT (CECT) scan (lesions with axial diameter ≥8 mm) were retrospectively analysed: all patients underwent 18F-FDG PET/CT within a mean 2 ± 1 months from CECT imaging. PET/CT was considered positive in the presence of abnormal FDG uptake in the pulmonary nodules and/or in other organs. The nature of lung nodules was defined at histopathology and/or imaging follow-up. Results: Fourteen (48%) patients showed negative and 15 (52%) positive PET/CT scan in the lungs: of these 15 patients, 7 (47%) had pathologic FDG-uptake in lungs only, whereas 8 (53%) showed abnormal FDG-uptake also in sites different from lungs. At histology and/or imaging follow-up, five (17%) patients were considered positive for BC lung metastases while in seven (24%) a second cancer was diagnosed. In this subset of patients, the sensitivity and specificity for FDG PET/CT in revealing lung lesions were 17% and 100%, respectively, for nodules

Trimethyltin nitriles either generated in situ or introduced directly readily react with carbonyl compounds to yield β-hydroxynitriles.

An uncatalyzed aldol-type reaction of aromatic N-trimethylsilyl ketene imines with O-protected α-trialkylsilyloxy or α-benzyloxy aldehydes is reported. It is shown that N-trimethylsilyl ketene imines (SKIs) are essential for the success of this aldol-type reaction, and that almost complete control of stereochemistry in the formation of the stereocentre vicinal to the stereogenic centre present in the starting aldehyde is seen when these compounds are used. A very high syn stereoselectivity was observed at room temperature, and a reversal of stereoselectivity to favour the formation of the anti product may be achieved at low temperature. Preliminary theoretical calculations support the hypothesis that the aldol-type reaction is facilitated by the formation of a cyclic transition state, with concomitant silatropic migration from the ketene imine-nitrogen to the aldehyde oxygen. The catalyst-free aldol reaction has been applied to aromatic N-trimethylsilyl ketene imines bearing two different aromatic groups. In these reactions, the diastereoselectivity for the stereocentre arising from aldehyde sp2 carbon remained extremely high, but the stereoselectivity for the formation of the new quaternary stereocentre was unsatisfactory.

The silyl ketimines, generated in situ from diarylmethane nitriles and TmsCl via lithiation, undergo a non-catalyzed reaction with isocyanates to give highly substituted malonamides in moderate yields.

Magnesium nitride is used as ammonia source for the Hantzsch synthesis of 1,4-dihydropyridines such as (III) having chiral alcohols in the ester functionality.

Optically active 3,4-disubsutituted azetidin-2-ones have been prepared by annelation of chiral silylimines derived from (S) or (R)-lactaldehyde with the ester enolate of the ethyl 2,2,5,5,-tetramethyl-1,2,5-azadisilolidin-1-acetate (STABASE). Oxidation of the hydroxyethyl side chain on the C-4 position of the β-lactam ring, followed by Baeyer-Villiger oxidation led to the optically active (3S, 4S ) 3-amino-4-acetoxy-β-laclam. The absolute configuration of this compound was determined by elaboration of this substrate to a key intermediate in the synthesis of the antibiotic “Aztreonam”. Nucleophilic displacement of the acetoxy group led to optically active 3-amino-4-alkyl (aryl)-azetidin-2-ones.

The N-trimethylsilyl imines of O-protected α-hydroxy aldehydes react with RCuMgXI BF 3 to give β-amino alcohols with high anti diastereoselectivity.

The title compound is obtained in high diastereomeric purity based on the stereoselective addition of trimethylsilylphosphite to N-trimethylsilylimine of (S) lactic aldehyde.

The title compound is obtained in high diastereomeric purity based on the stereoselective addition of trimethylsilyldibenzylphosphite (TMSDBP) to O-triisopropylsilyloxy(S)-lactaldehyde.

New analogs of cyclic amino acid-conjugated bile acids were synthesized, and their physicochemical and biological properties were compared with those of natural analogs. Ursodeoxycholic acid was amidated with D-proline, L-proline, 4-hydroxy-L-proline, and 4-methoxy-L-proline. Hyocholic and hyodeoxycholic acids were amidated with L-proline. The physicochemical properties were similar to those of the natural analogs. All of them were highly stable toward enzymatic C-24 amide bond hydrolysis and 7-dehydroxylation. Their transport, metabolism, and effect on biliary lipid secretion were evaluated in bile fistula rat after intravenous infusion. All the analogs were secreted in bile unmodified. The 4-methoxy-L-proline derivative produced the highest secretion rate, much higher than those of all the other natural and synthetic analogs. This was associated with a selective reduction of cholesterol secretion with normal phospholipid secretion and choleresis. When coinfused, all the analogs were able to prevent the hepatotoxicity induced by intravenous taurochenodeoxycholic acid, as revealed by normal choleresis, alkaline phosphatase, and lactate dehydrogenase values in bile. Considering the overall data, 4-methoxy-L-proline, 4-hydroxy-L-proline, and L-proline derivatives of ursodeoxycholic acid were more potent than the natural analogs.

The azetidinone 14 , a key intermediate in the synthesis of novel tribactam antibiotics ( e.g. 2 ) was obtained via condensation of an ester enolate with a N -trimethylsilylimine.

New conditions for the Staudinger reaction provide N -unsubstituted-3-phthalimido-β-lactams in satisfactory yields with complete trans-selectivity.

Stereocontrolled syntheses of 4-methoxy trinem 2 and its enantiomer 3 were achieved using the ester enolate N -trimethylsilylimine approach. The key step was the resolution of racemic enolphosphates derived from ephedrine.

An efficient synthesis of the lactonic derivative of 2,4-di- epi - polyoxamic acid, in high enantiomeric purity, through a hetero Diels-Alder approach, is reported.

Ring-closure of 1,3-azadienes to β-lactam rings is efficiently and quickly carried out under solvent-free conditions in an open-vessel microwave system. The synthesis of N-tert -butyldimethylsilyl azetidinones is reported.

A general approach to the solution phase parallel synthesis of perhydrooxazin-4-ones, which allows the preparation of milligram quantities of each individual member, is reported. An efficient purification method, using as “Sequestration Enabling Reagent” (SER) aminomethylpolystyrene resin in the presence of trimethylorthoformate is also described.

A new access to enantiopure 3-phthalimido-4-amino-5-(1-hydroxyalkyl) 1,5-dihydropyrrol-2-ones has been developed from 1,3-azadienes. Stereoselective Lewis acid catalyzed addition of a cyano group to an azadiene, followed by intramolecular ring closure, in a four-step one-pot synthesis, results in the formation of γ-lactams in satisfactory yields.