Existence of strong minimizers for the Griffith static fracture model in dimension two

We consider the Griffith fracture model in two spatial dimensions, and prove existence of strong minimizers, with closed jump set and continuously differentiable deformation fields. One key ingredient, which is the object of the present paper, is a generalization to the vectorial situation of the decay estimate by De Giorgi, Carriero, and Leaci. This is based on replacing the coarea formula by a method to approximate $SB{D}^p$ functions with small jump set by Sobolev functions, and is restricted to two dimensions. The other two ingredients will appear in companion papers and consist respectively in regularity results for vectorial elliptic problems of the elasticity type and in a method to approximate in energy $GSB{D}^p$ functions by $SB{V}^p$ ones.     

Development of a syn‐Selective Mannich Reaction of Aldehydes with Propargylic Imines by Dual Catalysis: Asymmetric Synthesis of Functionalized Propargylic Amines

Direct coupling of enolizable aldehydes with C‐alkynyl imines is realized affording the corresponding propargylic Mannich adducts of syn configuration, thus complementing previous methods that gave access to the anti‐isomers. The combination of proline and a urea Brønsted base cocatalyst is key for the reactions to proceed under very mild conditions (3–10 mol % catalyst loading, dichloromethane as solvent, ?20 °C, 1.2 molar equivalents of aldehyde) and with virtually total stereocontrol (syn/anti ratio up to 99:1; ee up to 99 %). Some possibilities of further chemical elaboration of adducts are also briefly illustrated.     

Correction to: Impact of leg bending in the patient-specific computational fluid dynamics of popliteal stenting

Acta Mechanica Sinica - A Correction to this paper has been published: https://doi.org/10.1007/s10409-021-01066-2     

Merging the Isonitrile-Tetrazine (4+1) Cycloaddition and the Ugi Four-Component Reaction into a Single Multicomponent Process

Multicomponent reactions are of utmost importance at generating a unique, wide, and complex chemical space. Herein we describe a novel multicomponent approach based on the combination of the isonitrile-tetrazine (4+1) cycloaddition and the Ugi four-component reaction to generate pyrazole amide derivatives. The scope of the reaction as well as mechanistic insights governing the 4H-pyrazol-4-imine tautomerization are provided. This multicomponent process provides access to a new chemical space of pyrazole amide derivatives and offers a tool for peptide modification and stapling.     

Metal Catalyzed Polymerization: From Stereoregular Poly(α-olefins) to Tailor-Made Biodegradable/Biorenewable Polymers and Copolymers

Metal catalyzed polymerizations are among the most important chemical reactions, accounting for the production of about 400 million tons per year of polymeric materials, 50 % of which are polyolefins. The CIRCC research units at the University of Salerno, founded by the late Professor Adolfo Zambelli, a coworker of Giulio Natta and a pioneer in the studies of stereospecific polymerization catalysts, has a consolidated expertise in this field. Although often considered a “mature” area of research, olefin polymerization catalysis continues to drive great interest of both industrial and academic scientists. On the other hand, strong political and economic pressure toward the development of “green” and possibly biodegradable alternatives to olefin-based polymers stimulated our group to direct increasing research efforts in the area of sustainable polymers. In this perspective, we focus on the most recent work from the CIRCC research units involved in homogeneous catalysis for polymerization of a variety of monomers, with the aim to address how the concepts and the expertise developed for olefin polymerization can be applied to the development of different metal-catalyzed polymerizations and copolymerizations. Of course, although the results are discussed in the frame of the most important literature contributions, a comprehensive review of such a wide and diversified topic is out of the scope of the paper. References to reviews covering the different types of metal catalyzed polymerizations are provided in each chapter.     

Organocatalytic,Asymmetric Eliminative [4+2] Cycloaddition of Allylidene Malononitriles with Enals: Rapid Entry to Cyclohexadiene‐Embedding Linear and Angular Polycycles

A direct aminocatalytic synthesis has been developed for the chemo‐, regio‐, diastereo‐, and enantioselective construction of densely substituted polycyclic carbaldehydes containing fused cyclohexadiene rings. The chemistry utilizes, for the first time, remotely enolizable π‐extended allylidenemalononitriles as electron‐rich 1,3‐diene precursors in a direct eliminative [4+2] cycloaddition with both aromatic and aliphatic α,β‐unsaturated aldehydes. The generality of the process is demonstrated by approaching 6,6‐, 5,6‐, 7,6‐, 6,6,6‐, and 6,5,6‐fused ring systems, as well as biorelevant steroid‐like 6,6,6,6,5‐ and 6,6,6,5,6‐rings. A stepwise reaction mechanism for the key [4+2] addition is proposed as a domino bis‐vinylogous Michael/Michael/retro‐Michael reaction cascade. The utility of the malononitrile moiety as traceless activating group of the dicyano nucleophilic substrates is demonstrated.