Rapid Assembly of Functionalised Spirocyclic Indolines by Palladium‐Catalysed Dearomatising Diallylation of Indoles with Allyl Acetate

Herein, we report the application of allyl acetate to the palladium‐catalysed dearomatising diallylation of indoles. The reaction can be carried out by using a readily available palladium catalyst at room temperature, and can be applied to a wide range of substituted indoles to provide access to the corresponding 3,3‐diallylindolinines. These compounds are versatile synthetic intermediates that readily undergo Ugi reactions or proline‐catalysed asymmetric Mannich reactions. Alternatively, acylation of the 3,3‐diallylindolinines with an acid chloride or a chloroformate, followed by treatment with aluminium chloride, enables 2,3‐diallylindoles to be prepared. By using ring‐closing metathesis, functionalised spirocyclic indoline scaffolds can be accessed from the Ugi products, and a dihydrocarbazole can be prepared from the corresponding 2,3‐diallylindole.     

Cyclodimerization versus Polymerization of Methyl Methacrylate Induced by N‐Heterocyclic Carbenes: A Combined Experimental and Theoretical Study

The activation behavior of two N‐heterocyclic carbenes (NHCs), namely, 1,3‐bis(isopropyl)imidazol‐2‐ylidene(NHCiPr) and 1,3‐bis(tert‐butyl) imidazol‐2‐ylidene (NHCtBu), as organic nucleophiles in the reaction with methyl methacrylate (MMA) is described. NHCtBu allows the polymerization of MMA in DMF at room temperature and in toluene at 50 °C, whereas NHCiPr reacts with two molecules of MMA, forming an unprecedented imidazolium–enolate cyclodimer (NHCiPr/MMA=1:2). It is proposed that the reaction mechanism occurs by initial 1,4‐nucleophilic addition of NHCiPr to MMA, generating a zwitterionic enolate 2 , followed by addition of 2 to a second MMA molecule, forming a linear imidazolium–enolate 3 (NHCiPr/MMA=1:2). Proton transfer, generating intermediate 5 , followed by cyclization and release of methanol yielded the aforementioned zwitterionic cyclodimer 1:2 adduct 7 , the molecular structure of which has been established by NMR spectroscopy, X‐ray diffraction, and mass spectrometry. This unexpected difference between NHCtBu and NHCiPr in the reaction with MMA (polymerization and cyclodimerization, respectively) can be rationalized by using DFT calculations. In particular, the nature of the NHC strongly influences the cyclodimerization pathway, the cyclization of 5 and the release of methanol are the discriminating step and limiting step, respectively. In the case of NHCtBu, both steps are strongly disfavoured compared with that of NHCiPr (energetic difference of around 14 and 9 kcal mol^?1, respectively), preventing the cyclization mechanism from a kinetic viewpoint. Moreover, addition of a third molecule of MMA in the polymerization pathway results in a lower activation barrier than that of the limiting step in the cyclodimerization pathway (difference of around 14 kcal mol^?1), in agreement with the formation of polymethyl methacrylate (PMMA) by using NHCtBu as nucleophile.     

Large Zero‐Field Splittings of the Ground Spin State Arising from Antisymmetric Exchange Effects in Heterometallic Triangles

[Ru₂Mn(O)(O₂CtBu)₆(py)₃] has an S=⁵/₂ ground state with a very large zero‐field splitting (ZFS) of D=2.9 cm^?1, as characterized by EPR spectroscopy at 4–330 GHz. This is far too large to be due to the Mn^II ion (D <0.2 cm^?1), as shown from the {Fe₂Mn} analogue, but can be modeled by antisymmetric exchange effects.     

Gelatin‐Alginate Gels and Their Enzymatic Modifications: Controlling the Delivery of Small Molecules

The release of molecules entrapped within biogels is dictated by diffusion laws. Innovative biogel architectures are conceived and tested to control small molecule delivery from gelatin gels. The ionic interactions modulate the release of small molecules. Alginate is then added to gelatin gels and further hydrolyzed; the influence of viscosity is discussed. Next, various mixed gels are compared, such as a gelatin‐alginate IPN and the original architecture of an alginate gel entrapped in a gelatin gel with or without a polysaccharidase. The relative influence of ionic interactions and diffusional constraints on the delivery of small charged molecules is explored, and a solution for controlling diffusion is proposed for any situation.

     

Analysis of a New Variational Model to Restore Point-Like and Curve-Like Singularities in Imaging

The paper is concerned with the analysis of a new variational model to restore point-like and curve-like singularities in biological images. To this aim we investigate the variational properties of a suitable energy which governs these pathologies. Finally in order to realize numerical experiments we minimize, in the discrete setting, a regularized version of this functional by fast descent gradient scheme.     

Adult zebrafish as a model organism for behavioural genetics

Recent research has demonstrated the suitability of adult zebrafish to model some aspects of complex behaviour. Studies of reward behaviour, learning and memory, aggression, anxiety and sleep strongly suggest that conserved regulatory processes underlie behaviour in zebrafish and mammals. The isolation and molecular analysis of zebrafish behavioural mutants is now starting, allowing the identification of novel behavioural control genes. As a result of this, studies of adult zebrafish are now helping to uncover the genetic pathways and neural circuits that control vertebrate behaviour.     

Studies of silicophosphate derivatives by 31P-->29Si CP MAS NMR

We show that it is possible to efficiently transfer magnetization from ³¹P to ²⁹Si, using variable amplitude CP MAS experiment. This experiment is demonstrated by using Si₅O(PO₄)₆, the synthesis protocol of which is described. From the obtained results, we show that the experiment allows the spectral edition of ²⁹Si spectra from ³¹P→²⁹Si CP, enabling the studies of derivatives involving Si–O–P linkages, such as phosphosilicate glasses, microporous silicoaluminophosphates (SAPO) and bioactive phosphosilicates.