Low-valent dialkoxytitanium(ii): a useful tool for the synthesis of functionalized seven-membered ring compounds.

Herein, we describe unprecedented access to all-carbon or heterocyclic seven-membered ring frameworks from 1,8-ene-ynes promoted by inexpensive low-valent titanium(ii) species, readily available from Ti(OiPr)4 and Grignard reagent. A broad range of cycloheptane, azepane or oxepane derivatives has been obtained (19 examples) with moderate to good yields and an excellent selectivity (up to 95/5 d.r.).

Enantioselective Gold(I)-Catalyzed Hydrative Cyclizations of N-Propargyl-ynamides into 3,6-Dihydropyridinones.

This study discloses the first enantioselective variant of the gold(I)-catalyzed hydrative cyclizations of ynamides, which have been implemented by using bis-gold(I) complexes of chiral diphosphines. Starting from N-propargyl-ynamides and water in the presence of p-toluenesulfonic acid, the cyclization reactions afford N-tosyl-3,6-dihydropyridin-2(1H)-ones in good isolated yields and with high levels of stereocontrol (20 examples, enantiomeric ratios up to 94:6).

A national atlas of tsetse and African animal trypanosomosis in Mali.

BACKGROUND: Tsetse-transmitted trypanosomosis is a deadly, neglected tropical disease and a major challenge for mixed crop-livestock agriculture in sub-Saharan Africa. It is caused by several species of the genus Trypanosoma. Information on the occurrence of tsetse flies and African animal trypanosomosis (AAT) is available for different areas of Mali. However, these data have never been harmonized and centralized, which prevents the development of comprehensive epidemiological maps and constrains an evidence-based planning of control actions. To address this challenge, we created a dynamic geo-spatial database of tsetse and AAT distribution in Mali. METHODS: A digital repository containing epidemiological data collected between 2000 and 2018 was assembled. In addition to scientific publications, the repository includes field datasheets, technical reports and other grey literature. The data were verified, harmonized, georeferenced and integrated into a single spatially-explicit database. RESULTS: For the tsetse component, approximately 19,000 trapping records, corresponding to 6000 distinct trapping locations and 38,000 flies were included in the database. Glossina palpalis gambiensis was the most widespread and abundant species, and it was found in the southern, southern-central and western parts of the country. Glossina tachinoides was only found in the South. Only a few specimens of Glossina morsitans submorsitans were detected. For the AAT component, approximately 1000 survey records were included, corresponding to 450 distinct survey sites and 37,000 tested bovines. AAT was found in all surveyed regions, although data for the tsetse-free North and North-East are lacking. Trypanosoma vivax and Trypanosoma congolense were the dominant species, while Trypanosoma brucei infections were much less numerous. CONCLUSIONS: The atlas of tsetse and AAT in Mali provides a synoptic view of the vector and disease situation at the national level. Still, major geographical gaps affect the North, the North-East and the West, and there is also a severe lack of data over the past five years. Trypanosomosis remains a major animal health problem in Mali. However, despite its prevalence and distribution, monitoring and control activities are presently very limited. Efforts should be made to strengthen the progressive control of AAT in Mali, and the atlas provides a new tool to identify priority areas for intervention.

Synthesis and X-ray diffraction study of a chiral bis-phosphahelicene palladium (II) complex.

As a complement to our previous studies on the development of a class of chiral phosphahelicenes, this article discloses the synthesis, spectroscopic, and structural characterizations of a new phosphahelicene transition metal complex. It demonstrates the ability of these hindered chiral ligands to coordinate Pd (II) in trans-complexes Cl2 Pd(L*)2 . In the solid state, the complex adopts a C2-symmetric arrangement with two ligands facing each other on the same face of the coordination plane. X-Ray data highlight bending of the Pd (II) unit from the expected planar coordination geometry that might be due to a significant π-π stacking effect between the central rings of two helical units.

Ti(II) and Rh(I) Complexes as Reagents toward a Thapsigargin Core.

A novel approach toward the [5-7]fused bicyclic core of thapsigargin, a subnanomolar inhibitor of the endo/sarcoplasmic calcium ATPase (SERCA), is presented. The synthetic route includes an original Ti(II)-mediated hydroxy-directed reductive coupling of an enantiomerically enriched propargylic alcohol and an intramolecular Rh(I)-catalyzed cyclocarbonylation reaction as key steps. Interestingly, through the first experiments of titanocene-mediated reductive cyclization of a 1,8-enyne, a seven-membered cycle was isolated as a unique product with a total diastereoselectivity.