Synthesis and crystal structures of palladium complexes based on α\alpha -amino-oximes derived from (RR)-limonene and their application in allylic alkylation of 1,3-dioxo compounds

Coordination compounds Pd(L1)Cl$_{2}$, Pd(L2)Cl$_{2}$, and Pd(L3)Cl$_{2}$ have been synthesized from optically pure $\alpha$-amino-oxime ligands L1–L3 based on $(R)$-limonene. Structures of the new palladium complexes are characterized and described by NMR spectroscopy and X-rays. These $\alpha$-amino-oxime ligands were then evaluated in the palladium-catalysed allylation of 1,3-dioxo compounds

Synthesis and crystal structures of palladium complexes based on α\alpha -amino-oximes derived from (RR)-limonene and their application in allylic alkylation of 1,3-dioxo compounds

Coordination compounds Pd(L1)Cl$_{2}$, Pd(L2)Cl$_{2}$, and Pd(L3)Cl$_{2}$ have been synthesized from optically pure $\alpha$-amino-oxime ligands L1–L3 based on $(R)$-limonene. Structures of the new palladium complexes are characterized and described by NMR spectroscopy and X-rays. These $\alpha$-amino-oxime ligands were then evaluated in the palladium-catalysed allylation of 1,3-dioxo compounds

The impact of surgical delay on resectability of colorectal cancer: An international prospective cohort study

AIM: The SARS-CoV-2 pandemic has provided a unique opportunity to explore the impact of surgical delays on cancer resectability. This study aimed to compare resectability for colorectal cancer patients undergoing delayed versus non-delayed surgery. METHODS: This was an international prospective cohort study of consecutive colorectal cancer patients with a decision for curative surgery (January-April 2020). Surgical delay was defined as an operation taking place more than 4 weeks after treatment decision, in a patient who did not receive neoadjuvant therapy. A subgroup analysis explored the effects of delay in elective patients only. The impact of longer delays was explored in a sensitivity analysis. The primary outcome was complete resection, defined as curative resection with an R0 margin. RESULTS: Overall, 5453 patients from 304 hospitals in 47 countries were included, of whom 6.6% (358/5453) did not receive their planned operation. Of the 4304 operated patients without neoadjuvant therapy, 40.5% (1744/4304) were delayed beyond 4 weeks. Delayed patients were more likely to be older, men, more comorbid, have higher body mass index and have rectal cancer and early stage disease. Delayed patients had higher unadjusted rates of complete resection (93.7% vs. 91.9%, P = 0.032) and lower rates of emergency surgery (4.5% vs. 22.5%, P < 0.001). After adjustment, delay was not associated with a lower rate of complete resection (OR 1.18, 95% CI 0.90-1.55, P = 0.224), which was consistent in elective patients only (OR 0.94, 95% CI 0.69-1.27, P = 0.672). Longer delays were not associated with poorer outcomes. CONCLUSION: One in 15 colorectal cancer patients did not receive their planned operation during the first wave of COVID-19. Surgical delay did not appear to compromise resectability, raising the hypothesis that any reduction in long-term survival attributable to delays is likely to be due to micro-metastatic disease

Outcomes from elective colorectal cancer surgery during the SARS-CoV-2 pandemic

This study aimed to describe the change in surgical practice and the impact of SARS-CoV-2 on mortality after surgical resection of colorectal cancer during the initial phases of the SARS-CoV-2 pandemic

Elective cancer surgery in COVID-19-free surgical pathways during the SARS-CoV-2 pandemic: An international, multicenter, comparative cohort study

PURPOSE As cancer surgery restarts after the first COVID-19 wave, health care providers urgently require data to determine where elective surgery is best performed. This study aimed to determine whether COVID-19–free surgical pathways were associated with lower postoperative pulmonary complication rates compared with hospitals with no defined pathway. PATIENTS AND METHODS This international, multicenter cohort study included patients who underwent elective surgery for 10 solid cancer types without preoperative suspicion of SARS-CoV-2. Participating hospitals included patients from local emergence of SARS-CoV-2 until April 19, 2020. At the time of surgery, hospitals were defined as having a COVID-19–free surgical pathway (complete segregation of the operating theater, critical care, and inpatient ward areas) or no defined pathway (incomplete or no segregation, areas shared with patients with COVID-19). The primary outcome was 30-day postoperative pulmonary complications (pneumonia, acute respiratory distress syndrome, unexpected ventilation). RESULTS Of 9,171 patients from 447 hospitals in 55 countries, 2,481 were operated on in COVID-19–free surgical pathways. Patients who underwent surgery within COVID-19–free surgical pathways were younger with fewer comorbidities than those in hospitals with no defined pathway but with similar proportions of major surgery. After adjustment, pulmonary complication rates were lower with COVID-19–free surgical pathways (2.2% v 4.9%; adjusted odds ratio [aOR], 0.62; 95% CI, 0.44 to 0.86). This was consistent in sensitivity analyses for low-risk patients (American Society of Anesthesiologists grade 1/2), propensity score–matched models, and patients with negative SARS-CoV-2 preoperative tests. The postoperative SARS-CoV-2 infection rate was also lower in COVID-19–free surgical pathways (2.1% v 3.6%; aOR, 0.53; 95% CI, 0.36 to 0.76). CONCLUSION Within available resources, dedicated COVID-19–free surgical pathways should be established to provide safe elective cancer surgery during current and before future SARS-CoV-2 outbreaks

Elective Cancer Surgery in COVID-19-Free Surgical Pathways During the SARS-CoV-2 Pandemic: An International, Multicenter, Comparative Cohort Study.

PURPOSE: As cancer surgery restarts after the first COVID-19 wave, health care providers urgently require data to determine where elective surgery is best performed. This study aimed to determine whether COVID-19-free surgical pathways were associated with lower postoperative pulmonary complication rates compared with hospitals with no defined pathway. PATIENTS AND METHODS: This international, multicenter cohort study included patients who underwent elective surgery for 10 solid cancer types without preoperative suspicion of SARS-CoV-2. Participating hospitals included patients from local emergence of SARS-CoV-2 until April 19, 2020. At the time of surgery, hospitals were defined as having a COVID-19-free surgical pathway (complete segregation of the operating theater, critical care, and inpatient ward areas) or no defined pathway (incomplete or no segregation, areas shared with patients with COVID-19). The primary outcome was 30-day postoperative pulmonary complications (pneumonia, acute respiratory distress syndrome, unexpected ventilation). RESULTS: Of 9,171 patients from 447 hospitals in 55 countries, 2,481 were operated on in COVID-19-free surgical pathways. Patients who underwent surgery within COVID-19-free surgical pathways were younger with fewer comorbidities than those in hospitals with no defined pathway but with similar proportions of major surgery. After adjustment, pulmonary complication rates were lower with COVID-19-free surgical pathways (2.2% v 4.9%; adjusted odds ratio [aOR], 0.62; 95% CI, 0.44 to 0.86). This was consistent in sensitivity analyses for low-risk patients (American Society of Anesthesiologists grade 1/2), propensity score-matched models, and patients with negative SARS-CoV-2 preoperative tests. The postoperative SARS-CoV-2 infection rate was also lower in COVID-19-free surgical pathways (2.1% v 3.6%; aOR, 0.53; 95% CI, 0.36 to 0.76). CONCLUSION: Within available resources, dedicated COVID-19-free surgical pathways should be established to provide safe elective cancer surgery during current and before future SARS-CoV-2 outbreaks

Synthèse de nouveaux ligands chiraux à partir de terpènes et applications en transfert d'hydrogène asymétrique

Les terpènes représentent plus de 80% des essences naturelles du Maroc, sont de faible coût et très abondants dans la nature, et existent sous forme optiquement pure. Ces composés, de par leur structure qui se prête facilement à des réactions de fonctionnalisations, comportent un ou plusieurs centres de chiralité qui les placent en première ligne comme précurseurs potentiels de coordinats optiquement actifs. Nous nous sommes intéressés à la synthèse de nouveaux ligands chiraux a partir de terpènes naturels. En particulier, nous avons préparé des aminoalcools, diimino et diaminodiols à partir de d a-pinène, et des a-aminooximes, leurs éthers ainsi que leurs diamines correspondantes à partir du limonène. Ces nouveaux coordinats chiraux ont ensuite été appliqués en catalyse asymétrique de transfert d hydrogène sur des cétones aromatiques sur des complexes à base de métaux de transition, en particulier le ruthénium, et en présence de l isopropanol comme source d hydrogène. Ces ligands en comparaison avec la littérature s avèrent performants en termes d activité et sont à même d induire une bonne énantiosélectivité (des excès énantiomériques de l ordre de 80% ont été obtenu sur certains substrats). Une étude plus approfondie du mécanisme réactionnel a été réalisée avec les ligands a-aminooximes, dont ce travail présente la première application en catalyse asymétrique.Terpenes represent more than 80% of natural oils of Morocco, are of moderate cost and very plentiful in nature. These compounds are prone to be readily functionalized, and as their backbone includes one or more chiral centers, they are therefore potential precursors for the synthesis of chiral ligands without separation of the enantiomers. In this work, we have been interested in the synthesis of novel chiral ligands from natural terpenes. In particular, we have prepared amino alcohols, diimino and diaminodiols from a-pinene, and a-aminooximes, their ethers and their corresponding diamines from limonene. These new ligands were applied in asymmetric catalysis of hydrogen transfer of aromatic ketones with complexes based on transition metals, particularly ruthenium, in the presence of isopropanol as hydrogen source. These ligands in comparison with the literature prove to be efficient in terms of activity and are shown to induce medium to good enantioselectivities (enantiomeric excesses up to 80% have been obtained on some substrates). Further study on the reaction mechanism have been carried out specifically with the a-aminooximes ligands, as this work is presenting the first application of this new series of ligands in asymmetric catalysis.LILLE1-Bib. Electronique (590099901) / SudocSudocFranceF

Chiral Ligands Derived from Monoterpenes: Application in the Synthesis of Optically Pure Secondary Alcohols via Asymmetric Catalysis

International audienc

α-Amino-Oximes Based on Optically Pure Limonene: A New Ligands Family for Ruthenium-Catalyzed Asymmetric Transfer Hydrogenation

International audienc

Chemical profile and in vitro antibacterial potential of essential oils and hydrolat extracts from aerial parts of three wild species of Moroccan Thymus

The present study aims to determine and compare the chemical composition of essential oils (EO) and hydrolat extracts (HE), isolated from three wild varieties of Moroccan thyme (T. satureioides Coss., T. willdenowii Boiss. and T. zygis L.) and to assess their antibacterial activity against four bacterial strains: Gram- (E. coli, Pr. Mirabilis) and Gram+ (B. subtilis, S. aureus). The findings showed that carvacrol (44.95%) and its biogenetic precursor p-cymene (23.36%) were the most dominant compounds of T. zygis L EO. The major volatile compounds in T. willdenowii Boiss EO were found to be thymol (42.38%), carvacrol (16.49%), and p-cymene (13.29%). Thus, T. satureioides Coss EO consists mainly of carvacrol (27.57%) and borneol (21.56%). On the other hand, carvacrol (72.33%) and thymol (10.70%) were the most prominent constituents in T. zygis L HE. T. willdenowii Boiss was dominated by thymol (65.01%) and carvacrol (21.74%). Furthermore, T. satureioides Coss HE was characterized by a high percentage of carvacrol (47.45%), borneol (25.04%), and γ-terpineol (19.34%). All investigated extracts exercised a strong antibacterial power against both tested Gram-positive and Gram-negative strains. However, the weakest activity was observed with T. satureioides Coss. EO and HE. The biological potential of HEs was found much higher than that of the corresponding EOs, which may give hydrolats a great value in aromatherapy to the detriment of essential oils