Type II Anion Relay Chemistry: Exploiting Bifunctional Weinreb Amide Linchpins for the One‐Pot Synthesis of Differentiated 1,3‐Diketones,Pyrans, and Spiroketals

The design, synthesis, and validation of new highly effective bifunctional linchpins for type II anion relay chemistry (ARC) has been achieved. The mechanistically novel negative‐charge migration that comprises the Brook rearrangement is now initiated by a stabilized tetrahedral intermediate, which is generated by nucleophilic addition to a Weinreb amide, rather than by a simple oxyanion that is generated from an epoxide. As a result, the linchpin preserves the carbonyl functionality in the ARC adducts, thus permitting access to functionally complex systems in a single flask without the need for further chemical manipulations. This tactic was validated with the one‐pot preparation of monoprotected 1,3‐diketones as well as pyran and spiroketal scaffolds, depending on the choice of nucleophile, electrophile, and work‐up conditions.     

Tweaking the acid-sensitivity of transiently thermoresponsive Polyacrylamides with cyclic acetal repeating units

Merging the characteristics of thermoresponsive and stimuli-degradable polymers yields so-called transiently thermoresponsive polymers, which can find application for the design of injectable gels, nanoparticles, etc. within a biomedical context. Among these polymers, only a limited number is reported which shows selective degradation under mild acidic conditions. However,extension of the library of transiently thermoresponsive polymers is desired to broadening the biomaterials toolbox to suit specific needs. Three monomers were developed by modification of 2-hydroxyethylacrylamide(HEAm) via tetrahydropyranylation or-furanylation with 3,4-dihydro-2 H-pyran(DHP), 2,3-dihydrofuran(DHF) or 2,3-dihydro-5-methylfuran(MeDHF). The presence of an acetal or ketal bond provided the monomers a pH-dependent hydrolysis behavior ranging from minutes to days. RAFT polymerisation allowed for the construction of homopolymers with temperature responsive behavior and pH-dependent hydrolysis which was strongly influenced by nature of the monomeric repeating units.     

The Reductive Dehydration of Cellulose by Solid/Gas Reaction with TiCl4 at Low Temperature: A Cheap,Simple, and Green Process for Preparing Anatase Nanoplates and TiO2/C Composites

Metal oxides and metal oxide/carbon composites are entering the development of new technologies and should therefore to be prepared by sustainable chemistry processes. Therefore, a new aspect of the reactivity of cellulose is presented through its solid/gas reaction with vapour of titanium(IV) chloride in anhydrous conditions at low temperature (80 °C). This reaction leads to two transformations both for cellulose and titanium(IV) chloride. A reductive dehydration of cellulose is seen at the lowest temperature ever reported and results in the formation of a carbonaceous fibrous solid as the only carbon‐containing product. Simultaneously, the in situ generation of water leads to the formation of titanium dioxide with an unexpected nanoplate morphology (ca. 50 nm thickness) and a high photocatalytic activity. We present the evidence showing the evolution of the cellulose and the TiO₂ nanostructure formation, along with its photocatalytic activity. This low‐temperature process avoids any other reagents and is among the greenest processes for the preparation of anatase and also for TiO₂/carbon composites. The anisotropic morphology of TiO₂ questions the role of the cellulose on the growing process of these nanoparticles.     

DYNAMIC STEREOCHEMISTRY OF SYMMETRICALLY BUT DIFFERENTLY SUBSTITUTED DIPHOSPHANES

Abstract

The main interest of our work in Bonn during the last years was in the field of phosphorus-carbon compounds with multiple bonds. Beside the synthesis of new classes of compounds we were particularly interested in the amazing analogy between the PC- and the CC-double bond, which could be proved by evidence of E/Z isomers and a clear indication of pericyclic reactions.     

Excited Brownian motions as limits of excited random walks

We obtain the convergence in law of a sequence of excited (also called cookies) random walks toward an excited Brownian motion. This last process is a continuous semi-martingale whose drift is a function, say ??, of its local time. It was introduced by Norris, Rogers and Williams as a simplified version of Brownian polymers, and then recently further studied by the authors. To get our results we need to renormalize together the sequence of cookies, the time and the space in a convenient way. The proof follows a general approach already taken by Tóth and his coauthors in multiple occasions, which goes through Ray-Knight type results. Namely we first prove, when ?? is bounded and Lipschitz, that the convergence holds at the level of the local time processes. This is done via a careful study of the transition kernel of an auxiliary Markov chain which describes the local time at a given level. Then we prove a tightness result and deduce the convergence at the level of the full processes.