Cyclisation reactions of bis-protected guanidines

The cyclisation of N-allyl- and N-homoallylguanidines using DMDO or I₂/K₂CO₂ leading to novel heterocycles is reported.     

NMR of some benzodiazepine drugs: Structure elucidation with lanthanide-induced shifts of N-1 substituted benzodiazepinones

Two 1,4-benzodiazepinones of psychopharmacological interest, pinazepam (2) and prazepam (3), were studied in solution by ¹³C and ¹H NMR. ¹H variable-temperature experiments showed that the seven-membered ring exists in a simple pseudo-boat form at room temperature, but the energy barrier is higher in 3 (ΔG_405°c = 82.8 kJ mol^?1) than in diazepam (1). Moreover, upon addition of LSR, the boat conformation is retained in the lanthanide ion-substrate complex, as with 1 in the solid state. Using a concentration-dependent shift technique and a computer-assisted LIS method, the conformations of the N-branched side-chain were investigated. Two preferred orientations were found for the propargyl group of 2, while three unequally populated conformations of the cyclopropyl moiety of 3 are distributed preferentially in the sterically unhindered space around the complex.     

Sun-reactive Skin Type in 4912 French adults participating in the SU.VI.MAX study

Phototype classifications were initially developed in an attempt to predict the skin reactions of patients to phototherapy and are now widely used to advise individuals with regard to sun protection. A transversal study was conducted on the SU.VI.MAX cohort to estimate the frequency of sun-reactive skin features in a large, general adult population-based sample, and to describe the associations between these features. The data were collected 3 years after the beginning of the SU.VI.MAX nutritional intervention study on 4912 volunteers (2868 women aged 35-60 years and 2044 men aged 45-60 years). A multiple correspondence analysis was performed to study the associations between the features. The results showed that these features correspond to a one-dimensional phenomenon, which allowed us to establish a score to summarize skin sensitivity to sun exposure. Furthermore, we found a link between gender and phototype using the Césarini classification (phototype > or = IV: 37% of women, 47% of men). The analysis of the relationship with sun-reactive skin features and the score revealed the same trend. Phenotypic evaluation appears to be a good estimator of skin sensitivity to sun exposure for clinical screening or for use in research, and is easy to collect at a lower cost. Moreover, the sun sensitivity difference between gender should be considered in education about photoprotection.     

Synthesis of multi-1,10-phenanthroline ligands with 1,3-phenylene linkers and their lithium complexes

The synthesis of two multisite ligands containing four and five 1,10-phenanthroline (phen) chelates in line, respectively, is presented. The connectors are 1,3-phenylene linkers. The two ligands were prepared following multistep procedures, the two key reactions being the Suzuki coupling reaction between aromatic nuclei and the nucleophilic addition of aryllithium derivatives onto a phen fragment. The coordination chemistry of both ligands with Li+ ions was very clean and selective, whereas their reaction with copper(I) led to intractable mixtures of insoluble complexes. The tetraphen and the pentaphen compounds afforded almost quantitatively the four- and five-lithium double-stranded helical complexes, respectively. The helical systems are probably highly wound, as indicated by NMR measurements. The pronounced strain of the 5-Li+ complex is reflected by the easy loss of a lithium cation, as shown by electrospray mass spectrometry.