Allyl Cyanate/Isocyanate Rearrangement in Glycals: Stereoselective Synthesis of 1-Amino and Diamino Sugar Derivatives.

The [3,3]-sigmatropic allyl cyanate/isocyanate rearrangement of glycals in the presence of O-, N-, and C-nucleophiles afforded ß-N-glucosyl and galactosyl carbamates, ureas, and amides in good yields. The unsaturated products were elaborated to N-glycosides by dihydroxylation, to 1,3-diaminosugars by tethered aminohydroxylation, or to 1,2-diaminosugars by iteration of the sigmatropic rearrangement. This metal-free methodology represents an excellent and general method for the stereoselective synthesis of N-glycosides and diamino sugars with complete transmission of stereochemical information.

Increase of pneumococcal serotype 19A in Italy is due to expansion of the piliated clone ST416/CC199.

The emergence of Streptococcus pneumoniae serotype 19A, following use of the heptavalent pneumococcal conjugate vaccine (PCV7), has been favoured by multiple antibiotic resistance of this serotype and by other unknown factors. The aim of this study was to examine 19A isolates from invasive pneumococcal diseases (IPD) obtained before and after PCV7 implementation to ascertain which characteristics, including the presence of pili, might have favoured the emergence of this serotype in Italy. All S. pneumoniae isolates from IPD collected at the Italian National Institute of Health in the years 2001-2003 and 2006-2009 were serotyped. The 19A isolates were submitted to antimicrobial susceptibility testing by Etest and were genotyped by a combination of pulsed field gel electrophoresis (PFGE) and Multi Locus Sequence Typing (MLST). The presence of the pilus islets PI-1 and PI-2 was detected by PCR assays targeting a marker gene in each islet. The proportion of 19A isolates from IPD significantly increased from 4 % in 2001-2003 to 12 % in 2006-2009. This was largely due to the expansion of a clone characterized by sequence type (ST) 416, clonal complex (CC) 199, already present in Italy before PCV7 implementation. This clone included isolates susceptible to penicillin and containing PI-1 genes. Other CCs contributed to the emergence of serotype 19A: CC63 and CC193, already present in 2001-2003, and new-emerging CCs or clones such as CC230, CC320 and ST5204, that include drug-resistant and/or pilus-positive isolates. The expansion of serotype 19A in Italy might have been favoured not only by antibiotic resistance, but also by other bacterial factors such as the presence of pili.