Construction of β‑Oximino Phosphorodithioates via (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl-Promoted Difunctionalization of Alkenes with <i>tert</i>-Butyl Nitrite, P₄S₁₀, and Alcohols

A (2,2,6,6-tetramethylpiperidin-1-yl)­oxyl-mediated difunctionalization of alkenes with tert-butyl nitrite, P4S10, and alcohols has been developed for the synthesis of β-oximino phosphorodithioates. The reaction goes through a radical pathway with the successive installation of phosphorodithioate and an oxime group. This four-component protocol offers a practical approach to constructing a variety of β-oximino phosphorodithioates in moderate to good yields with favorable functional group tolerance

The average pass rate and average excellent rate of experimental group and control group.

<p>The average pass rate and average excellent rate of experimental group and control group.</p

Biomimetic Dynamic Kinetic Asymmetric <i>N</i>‑Oxidation with H₂O₂ and O₂

Optically active chiral sulfoxides, phosphine oxides, and amine oxides are ubiquitous in pharmaceutical and asymmetric synthesis. However, unlike the well-developed synthetic method for chiral sulfoxides and phosphine oxides, routes to N-chiral amine oxides have garnered less attention due to the instability of the N-centers in tertiary amines. So far, resolution and asymmetric induction are still the main strategies for N-chiral amine oxides, while asymmetric N-oxidation is only limited to several underdeveloped enzymatic and metal-catalyzed processes. Here, we develop an efficient biomimetic asymmetric N-oxidation method by designing various chiral alloxan catalysts to mimic the flavin-containing monooxygenases in vivo, which presents an entry into N-chirality control. With H2O2 or O2 as an eco-friendly oxidant, a range of N-chiral acyclic tertiary amine oxides were obtained in high yields (up to 98%) and with ee values (up to 93%). Control experiments and density functional theory (DFT) calculations revealed this successful stereocontrol might rely on hydrogen-bond-mediated dynamic kinetic resolution

Espace Numérique de Travail en collège : étude sur la formation des enseignants

International audienceL’article présente une analyse de discours d’enseignants qui expérimentent un espace numérique de travail au sein de leur établissement. L’étude questionne la formation de prise en main de cet ENT mis en place. Il ressort de l’analyse que pour pouvoir amorcer une phase d’appropriation de l’ENT par les enseignants et les autres acteurs, des cadres de niveaux national et local sont encore à construire

Literature screening process and results.

<p>Literature screening process and results.</p

Meta-regression of the effects of confounding factors on pass rate, excellent rate and examination score.

<p>Meta-regression of the effects of confounding factors on pass rate, excellent rate and examination score.</p

Video1_Case report: A rare case of anomalous origin of the left coronary artery from the pulmonary artery accompanied with unilateral absence of pulmonary artery in an adult patient.avi

Both the anomalous origin of the left coronary artery from the pulmonary artery (ALCAPA) and unilateral absence of the pulmonary artery (UAPA) are rare congenital malformations, ALCAPA accompanied with UAPA is extremely rare. Here, we reported a middle-aged man admitted to our department for evaluation of chest pain during exercise. Physical examination and lab tests did not unveil obvious abnormality; however, transthoracic echocardiogram (TTE) revealed multivessel myocardial collateral blood flow signals in the left ventricular wall and ventricular septum, a shunting flow from the left coronary artery into the pulmonary artery and dilated right coronary artery (RCA), which supported but did not confirm the diagnosis of ALCAPA. Coronary angiography (CAG) showed an absent left coronary ostium and a dilated RCA, with extensive collaterals supplying the left coronary system. Multidetector computed tomography angiography (MDCTA) was then performed and revealed the anomalous origin of the left main coronary artery (LMCA) arising from the pulmonary artery, and it incidentally unveiled another rare congenital malformation of UAPA. The patient underwent surgical correction of ALCAPA by reimplantation of the LMCA to the aorta, without surgical treatment of UAPA. The patient had been in good clinical condition and remained angina free with good exercise tolerance during follow-up (∼6 months so far). In this case, we discussed the diagnostic value of TTE, CAG, and MDCTA on rare abnormalities as ALCAPA and UAPA. We highlighted the role of multiple non-invasive imaging modalities in diagnosing rare causes of angina in adult patients, and the importance of careful examination in avoiding misdiagnosis. To our best knowledge, this is the first report of ALCAPA accompanied with UAPA in an adult patient.</p

Video2_Case report: A rare case of anomalous origin of the left coronary artery from the pulmonary artery accompanied with unilateral absence of pulmonary artery in an adult patient.avi

Both the anomalous origin of the left coronary artery from the pulmonary artery (ALCAPA) and unilateral absence of the pulmonary artery (UAPA) are rare congenital malformations, ALCAPA accompanied with UAPA is extremely rare. Here, we reported a middle-aged man admitted to our department for evaluation of chest pain during exercise. Physical examination and lab tests did not unveil obvious abnormality; however, transthoracic echocardiogram (TTE) revealed multivessel myocardial collateral blood flow signals in the left ventricular wall and ventricular septum, a shunting flow from the left coronary artery into the pulmonary artery and dilated right coronary artery (RCA), which supported but did not confirm the diagnosis of ALCAPA. Coronary angiography (CAG) showed an absent left coronary ostium and a dilated RCA, with extensive collaterals supplying the left coronary system. Multidetector computed tomography angiography (MDCTA) was then performed and revealed the anomalous origin of the left main coronary artery (LMCA) arising from the pulmonary artery, and it incidentally unveiled another rare congenital malformation of UAPA. The patient underwent surgical correction of ALCAPA by reimplantation of the LMCA to the aorta, without surgical treatment of UAPA. The patient had been in good clinical condition and remained angina free with good exercise tolerance during follow-up (∼6 months so far). In this case, we discussed the diagnostic value of TTE, CAG, and MDCTA on rare abnormalities as ALCAPA and UAPA. We highlighted the role of multiple non-invasive imaging modalities in diagnosing rare causes of angina in adult patients, and the importance of careful examination in avoiding misdiagnosis. To our best knowledge, this is the first report of ALCAPA accompanied with UAPA in an adult patient.</p

Development of an Enzymatic Process for the Synthesis of (<i>S</i>)‑2-Chloro-1-(2,4-dichlorophenyl) Ethanol

(S)-2-Chloro-1-(2,4-dichlorophenyl) ethanol (3) is a chiral intermediate in the synthesis of luliconazole ((R)-E-1). Here, we report a novel biopreparation of 3 by bioreduction of 2-chloro-1-(2,4-dichlorophenyl) ethanone (2) using recombinant Escherichia coli expressing LK08, a ketoreductase mutant from Lactobacillus kefiri, as a biocatalyst. The reaction conditions for the biotransformation including pH, temperature, and concentration of isopropanol and NADP+, as well as the amount of recombinant E. coli cells, were optimized to improve the process productivity. When the enzymatic process was carried out on a 300 g scale under the optimized conditions, the ketone 2 was fully converted to chiral alcohol 3 with a product ee value of >99%. Furthermore, 3 was isolated and used to chemically synthesize luliconazole with 38% yield and 99% ee. This study presents an efficient and cost-effective chemoenzymatic process for the production of (R)-E-1