Dearomatization of 3-Nitroindoles with Highly γ-Functionalized Allenoates in Formal (3+2) Cycloadditions

3-Nitroindoles are easily reacted with highly substituted γ-allenoates in the presence of a commercially available phosphine catalyst. For instance, allenoates derived from biomolecules such as amino and deoxycholic acids are combined for the first time with 3-nitroindole. The corresponding dearomatized (3+2) tricyclic cycloadducts are obtained as α-regioisomers exclusively. DFT computations shed light on this multi-step reaction mechanism and on the selectivities observed in the sequence.     

Controlled release and long-term antibacterial activity of chlorhexidine digluconate through the nanoporous network of microfibrillated cellulose

The recent study focusing on paper coated with microfibrillated cellulose (MFC) revealed the ability of such a structure to achieve a controlled release of molecules introduced into its nanoporous network. The present study examines this concept using a chlorhexidine digluconate-based (CHX) antibacterial solution. Various analyses were performed, optical microscopy, FE-SEM and AFM to underline the structure of the nanoporous MFC network. Release studies were conducted in an aqueous medium following two different protocols and antibacterial tests were done to evaluate the efficiency of the final materials obtained. MFC coating provided a slower and more progressive release of CHX. Indeed, papers impregnated with CHX were active for 18 days, whereas papers coated with CHX/MFC retained their antibacterial activity for 45 days. In parallel, similar tests were carried out using a model coating slurry, and although the rate of release of CHX was also slowed down, the quantities released were insufficient to confer any antibacterial activity. In conclusion, this study suggests that the use of MFC as a coating could be very promising since it allows a controlled and progressive release of molecules preserving long-term antibacterial activity.     

Alcohol uncaging with fluorescence reporting: evaluation of o-acetoxyphenyl methyloxazolone precursors

This paper evaluates a series of photolabile protecting groups with built-in fluorescence reporting. They rely on readily available o-acetoxyphenyl methyloxazolones as activated precursors. Alcohol substrates are easily caged. The resulting photoactivable esters exhibit large one- and two-photon uncaging cross sections. The alcohol substrates are quantitatively released in a 1:1 molar ratio with a strongly fluorescent coumarin coproduct that serves as a reporter to quantify substrate delivery.     

Convenient method for the rapid generation of highly active and enantioselective yttrium catalysts for asymmetric hydroamination

A facile method for the preparation of highly active and enantioselective yttrium precatalysts for asymmetric hydroamination of gem-disubstituted aminoalkenes, from the combination of YCl(3) or YCl(3)(THF)(3.5) with ligand (R)- and n-BuLi is described.     

Transannular rearrangement of activated 2,5-diketopiperazines: a key route to original scaffolds

An efficient and original stereocontrolled transannular rearrangement starting from activated 2,5-diketopiperazines has been developed, an opportunity for the medicinal chemistry field, which requests access to novel biological scaffolds. This powerful ring contraction, which can be related to a stereoselective aza-version of the Chan rearrangement, allows for example the one-step synthesis of various tetramic acids, access to 2-disubstituted statins, or the synthesis of relevant lactam-constrained dipeptide mimetics using a TRAL-RCM sequence.     

Highly efficient, base-catalysed, intramolecular hydroamination of non-activated olefins

The intramolecular hydroamination of a large variety of non-activated alkenes can be efficiently catalysed by small amounts of lithium bases, providing smoothly and in high yields the corresponding five- and six-membered ring heterocycles. Fused and bridged bicyclic amines, of varying ring sizes, can be readily prepared either by a sequential hydroamination process or by a tandem, double addition reaction.     

Improved microwave steam distillation apparatus for isolation of essential oils. Comparison with conventional steam distillation

Steam distillation (SD) is routinely used by analysts for the isolation of essential oils from herbs, flowers and spices prior to gas chromatographic analysis. In this work, a new process design and operation for an improved microwave steam distillation (MSD) of essential oils from aromatic natural products was developed. To demonstrate its feasibility, MSD was compared with the conventional technique, SD, for the analysis of volatile compounds from dry lavender flowers (Lavandula angustifolia Mill., Lamiaceae). Essential oils isolated by MSD were quantitatively (yield) and qualitatively (aromatic profile) similar to those obtained by SD, but MSD was better than SD in terms of rapidity (6 min versus 30 min for lavender flowers), thereby allowing substantial savings of costs in terms of time and energy. Lavender flowers treated by MSD and SD were observed by scanning electron microscopy. Micrographs provide evidence of more rapid opening of essential oil glands treated by MSD, in contrast to conventional SD.