Photoredox Catalytic Pentafluorosulfanylative Domino Cyclization of α-Substituted Alkenes to Oxaheterocycles by Using SF6_{6}

Virtually inert sulfur hexafluoride becomes a precious pentafluorosulfanylation agent, if properly activated by photoredox catalysis, to access α-fluoro and α-alkoxy SF$_{5}$-compounds. This advanced protocol converts SF$_{6}$ in the presence of alkynols as bifunctional C−C- and C−O-bond forming reagents directly into pentafluorosulfanylated oxygen-containing heterocycles in a single step from α-substituted alkenes. The proposed mechanism is supported by theoretical calculations and gives insights not only in the pentafluorosulfanylation step but also into formation of the carbon-carbon bond and is in full agreement with Baldwin\u27s cyclization rules. The key step is a radical type 5-, 6- respectively 7-exo-dig-cyclization. The synthesized oxaheterocycles cannot be simply prepared by other synthetic methods, show a high level of structural complexity and significantly expand the scope of pentafluorosulfanylated building blocks valuable for medicinal and material chemistry

Heterobimetallic Gold/Ruthenium Complexes Synthesized via Post‐functionalization and Applied in Dual Photoredox Gold Catalysis

The synthesis of heterobimetallic AuI/RuII complexes of the general formula syn- and anti-[{AuCl}(L1∩L2){Ru(bpy)$_{2}$}][PF$_{6}$]$_{2}$ is reported. The ditopic bridging ligand L1∩L2 refers to a P,N hybrid ligand composed of phosphine and bipyridine substructures, which was obtained via a post-functionalization strategy based on Diels-Alder reaction between a phosphole and a maleimide moiety. It was found that the stereochemistry at the phosphorus atom of the resulting 7-phosphanorbornene backbone can be controlled by executing the metal coordination and the cycloaddition reaction in a different order. All precursors, as well as the mono- and multimetallic complexes, were isolated and fully characterized by various spectroscopic methods such as NMR, IR, and UV-vis spectroscopy as well as cyclic voltammetry. Photophysical measurements show efficient phosphorescence for the investigated monometallic complex anti-[(L1∩L2){Ru(bpy)$_{2}$}][PF$_{6}$]$_{2}$ and the bimetallic analogue syn-[{AuCl}(L1∩L2){Ru(bpy)$_{2}$}][PF$_{6}$]$_{2}$, thus indicating a small influence of the {AuCl} fragment on the photoluminescence properties. The heterobimetallic Au$^{I}$/Ru$^{II}$ complexes syn- and anti-[{AuCl}(L1∩L2){Ru(bpy)$_{2}$}][PF$_{6}$]$_{2}$ are both active catalysts in the P-arylation of aryldiazonium salts promoted by visible light with H-phosphonate affording arylphosphonates in yields of up to 91 %. Both dinuclear complexes outperform their monometallic counterparts

Multistimuli‐Responsive [3]Dioxaphosphaferrocenophanes with Orthogonal Switches

Novel multistimuli-responsive phosphine ligands comprising a redox-active [3]dioxaphosphaferrocenophane backbone and a P-bound imidazolin-2-ylidenamino entity that allows switching by protonation are reported. Investigation of the corresponding metal complexes and their redox behaviour are reported and show the sensitivity of the system towards protonation and metal coordination. The experimental findings are supported by DFT calculations. Protonation and oxidation events are applied in Rh-catalysed hydrosilylations and demonstrate a remarkable influence on reactivity and/or selectivity

Cooperative effects in multimetallic complexes applied in catalysis

The field of multimetallic catalysis is rapidly developing and some multimetallic complexes catalyze organic transformations to yield the desired products in more efficient ways owing to the combined action of different metals in a cooperative fashion. This Concept article describes the recent advances of cooperative catalysis playing in multimetallic systems such as homo‐multimetallic complexes with short metal‐metal distances, homo‐multimetallic complexes with long metal‐metal distances, hetero‐multimetallic complexes and metallocene‐based multimetallic complexes with special attention towards redox‐switchable catalysis. Examples are illustrated in which the use of multimetallic complexes show clear enhancement of catalytic outcomes when compared with the sum of their corresponding mononuclear counterparts. Furthermore, several examples are discussed showing the effects of electronic communication in cooperative systems.Collaborative Research Centre CRC/Transregio 88DST-SERBProjekt DEA

Synthesis of Thiophene‐fused Helicenes

The synthesis of three penta- and three hexahelicenes containing two terminal thiophene units is described. The syntheses of pentahelicenes consist of 1,4-bisalkynylation of a benzene precursor and double Suzuki coupling in 2,3-position to introduce thiophene units. The ortho,ortho’ fusion yielding the final products was achieved with Fürstner\u27s protocol using platinum(II) chloride or JohnPhos-complexed gold(I) as catalysts. A similar approach to hexahelicenes started with a naphthalene derivative, where 2,7-bisalkynylation and subsequent double Suzuki coupling with thiophene-2-boronic acid at 1,8-position furnished precursors, in which ortho,ortho’ fusion to the respective hexahelicenes was achieved with platinum(II) chloride or, favourably, with indium(III) chloride. UV/Vis spectra and cyclic voltammograms were recorded for all helicenes and HOMO/LUMO gaps were calculated with DFT methods

Body wall structure in the starfish Asterias rubens

Queen Mary University of London; Engineering & Physical Sciences Research Council. Grant Number: EP/J501360/1; Biotechnology and Biological Sciences Research Council. Grant Number: BBSRC;BB/M001644/1; Royal Society through the Equipment Grant scheme. Grant Number: SEMF1A6

Diverse and productive source of biopolymer inspiration: marine collagens

Marine biodiversity is expressed through the huge variety of vertebrate and invertebrate species inhabiting intertidal to deep-sea environments. The extraordinary variety of â forms and functionsâ  exhibited by marine animals suggests they are a promising source of bioactive molecules and provides potential inspiration for different biomimetic approaches. This diversity is familiar to biologists and has led to intensive investigation of metabolites, polysaccharides, and other compounds. However, marine collagens are less well-known. This review will provide detailed insight into the diversity of collagens present in marine species in terms of their genetics, structure, properties, and physiology. In the last part of the review the focus will be on the most common marine collagen sources and on the latest advances in the development of innovative materials exploiting, or inspired by, marine collagens.The authors are grateful for the financial support from European Union, under the scope of European Regional Development Fund((ERDF) through the POCTEP project 0687_NOVOMAR_1_P and Structured Project NORTE-01- 0145-FEDER-000021 and from the Portuguese Foundation for Science and Technology (FCT), under the scope of the BiogenInk project (M-ERA-NET2/0022/2016) and from the European Cooperation in Science & Technology program (EU COST). Grant title: “Stem cells of marine/aquatic inverte brates: from basic research to innovative applications” (MARISTEM). MSR acknowledges FCT for the Ph.D. scholarship (PD/BD/143091/2018)