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- ItemPd/Cu-Catalyzed amide-enabled selectivity-reversed borocarbonylation of unactivated alkenes(Cambridge : RSC, 2021) Wu, Fu-Peng; Wu, Xiao-FengThe addition reaction between CuBpin and alkenes to give a terminal boron substituted intermediate is usually fast and facile. In this communication, a selectivity-reversed procedure has been designed and established. This selectivity-reversed borocarbonylation reaction is enabled by a cooperative action between palladium and copper catalysts and proceeds with complete regioselectivity. The key to the success of this transformation is the coordination of the amide group and slower CuBpin formation by using KHCO3as the base. A wide range of β-boryl ketones were produced from terminal unactivated aliphatic alkenes and aryl iodides. Further synthetic transformations of the obtained β-boryl ketones have been developed as well. © The Royal Society of Chemistry 2021.
- ItemA general strategy for the synthesis of α-trifluoromethyl- and α-perfluoroalkyl-β-lactams via palladium-catalyzed carbonylation(Cambridge : RSC, 2021) Li, Yang; Zhang, Cai-Lin; Huang, Wei-Heng; Sun, Ning; Hao, Meng; Neumann, Helfried; Beller, Matthiasβ-Lactam compounds play a key role in medicinal chemistry, specifically as the most important class of antibiotics. Here, we report a novel one-step approach for the synthesis of α-(trifluoromethyl)-β-lactams and related products from fluorinated olefins, anilines and CO. Utilization of an advanced palladium catalyst system with the Ruphos ligand allows for selective cycloaminocarbonylations to give diverse fluorinated β-lactams in high yields. © The Royal Society of Chemistry 2021.
- ItemAldehydes and ketones influence reactivity and selectivity in nickel-catalysed Suzuki-Miyaura reactions(Cambridge : RSC, 2020) Cooper, Alasdair K.; Leonard, David K.; Bajo, Sonia; Burton, Paul M.; Nelson, David J.The energetically-favorable coordination of aldehydes and ketones-but not esters or amides-to Ni0 during Suzuki-Miyaura reactions can lead either to exquisite selectivity and enhanced reactivity, or to inhibition of the reaction. Aryl halides where the C-X bond is connected to the same π-system as an aldehyde or ketone undergo unexpectedly rapid oxidative addition to [Ni(COD)(dppf)] (1), and are selectively cross-coupled during competition reactions. When aldehydes and ketones are present in the form of exogenous additives, the cross-coupling reaction is inhibited to an extent that depends on the strength of the coordination of the pendant carbonyl group to Ni0. This work advances our understanding of how common functional groups interact with Ni0 catalysts and how these interactions affect workhorse catalytic reactions in academia and industry. This journal is © The Royal Society of Chemistry.
- ItemFractography of poly(: N -isopropylacrylamide) hydrogel networks crosslinked with mechanofluorophores using confocal laser scanning microscopy(Cambridge : RSC Publ., 2020) Stratigaki, Maria; Baumann, Christoph; van Breemen, Lambert C.A.; Heuts, Johan P.A.; Sijbesma, Rint P.; Göstl, RobertDue to their soft and brittle nature, the mechanical characterization of polymer hydrogels is a difficult task employing traditional testing equipment. Here, we endowed poly(N-isopropyl acrylamide) (PNIPAAm) hydrogel networks with Diels-Alder adducts of π-extended anthracenes as mechanofluorophore crosslinkers. After swelling the networks with varying amounts of water and subjecting them to force, we visualized the subsequent fluorescence caused by covalent bond scission with confocal laser scanning microscopy (CLSM) and related the intensities to the macroscopic fracture mechanics and the elastic moduli recorded with traditional uniaxial compression. The sensitivity of the mechanofluorophores allowed the analysis of low levels of mechanical stress produced via a hand-induced needle-puncturing process and, thus, is an alternative to conventional force application methods. The detection and precise localization of covalent bond scission via CLSM helps elucidating the interrelationship between molecular structure and the macroscopic properties of chemically crosslinked polymeric hydrogels. We believe that this micro-scale mechanophore-assisted fractography can establish a new paradigm for the mechanical analysis of soft matter in fields covering traditional polymer and life sciences. © 2019 The Royal Society of Chemistry.
- ItemNanoscale disintegration kinetics of mesoglobules in aqueous poly(N-isopropylacrylamide) solutions revealed by small-angle neutron scattering and pressure jumps(Cambridge : RSC Publ., 2021) Niebuur, Bart-Jan; Chiappisi, Leonardo; Jung, Florian A.; Zhang, Xiaohan; Schulte, Alfons; Papadakis, Christine M.Identification and control of the disintegration mechanism of polymer nanoparticles are essential for applications in transport and release including polymer delivery systems. Structural changes during the disintegration of poly(N-isopropylacrylamide) (PNIPAM) mesoglobules in aqueous solution are studied in situ and in real time using kinetic small-angle neutron scattering with a time resolution of 50 ms. Simultaneously length scales between 1 and 100 nm are resolved. By initiating phase separation through fast pressure jumps across the coexistence line, 3 wt% PNIPAM solutions are rapidly brought into the one-phase state. Starting at the same temperature (35.1 °C) and pressure (17 MPa) the target pressure is varied over the range 25–48 MPa, allowing to systematically alter the osmotic pressure of the solvent within the mesoglobules. Initially, the mesoglobules have a radius of gyration of about 80 nm and contain a small amount of water. Two disintegration mechanisms are identified: (i) for target pressures close to the coexistence line, single polymers are released from the surface of the mesoglobules, and the mesoglobules decrease in size, which takes ∼30 s. (ii) For target pressures more distant from the coexistence line, the mesoglobules are swollen by water, and subsequently the chains become more and more loosely associated. In this case, disintegration proceeds within less than 10 s, controlled by the osmotic pressure of the solvent.