3792-53-8Relevant articles and documents
Photocontrolled Cobalt Catalysis for Selective Hydroboration of α,β-Unsaturated Ketones
Beltran, Frédéric,Bergamaschi, Enrico,Funes-Ardoiz, Ignacio,Teskey, Christopher J.
supporting information, p. 21176 - 21182 (2020/09/17)
Selectivity between 1,2 and 1,4 addition of a nucleophile to an α,β-unsaturated carbonyl compound has classically been modified by the addition of stoichiometric additives to the substrate or reagent to increase their “hard” or “soft” character. Here, we demonstrate a conceptually distinct approach that instead relies on controlling the coordination sphere of a catalyst with visible light. In this way, we bias the reaction down two divergent pathways, giving contrasting products in the catalytic hydroboration of α,β-unsaturated ketones. This includes direct access to previously elusive cyclic enolborates, via 1,4-selective hydroboration, providing a straightforward and stereoselective route to rare syn-aldol products in one-pot. DFT calculations and mechanistic experiments confirm two different mechanisms are operative, underpinning this unusual photocontrolled selectivity switch.
Synthesis and Biochemical Evaluation of Nicotinamide Derivatives as NADH Analogue Coenzymes in Ene Reductase
Falcone, Natashya,She, Zhe,Syed, Jebreil,Lough, Alan,Kraatz, Heinz-Bernhard
, p. 838 - 845 (2019/02/07)
Nicotinamide and pyridine-containing conjugates have attracted a lot of attention in research as they have found use in a wide range of applications including as redox flow batteries and calcium channel blockers, in biocatalysis, and in metabolism. The interesting redox character of the compounds’ pyridine/dihydropyridine system allows them to possess very similar characteristics to the natural chiral redox agents NAD+/NADH, even mimicking their functions. There has been considerable interest in designing and synthesizing NAD+/NADH mimetics with similar redox properties. In this research, three nicotinamide conjugates were designed, synthesized, and characterized. Molecular structures obtained through X-ray crystallography were obtained for two of the conjugates, thereby providing more detail on the bonding and structure of the compounds. The compounds were then further evaluated for biochemical properties, and it was found that one of the conjugates possessed similar functions and characteristics to the natural NADH. This compound was evaluated in the active enzyme, enoate reductase; like NADH, it was shown to help reduce the C=C double bond of three substrates and even outperformed the natural coenzyme. Kinetic data are reported.
Heteropoly acid catalysis for the isomerization of biomass-derived limonene oxide and kinetic separation of the trans-isomer in green solvents
Cotta, Rafaela F.,Martins, Rafael A.,Pereira, Matheus M.,da Silva Rocha, Kelly A.,Kozhevnikova, Elena F.,Kozhevnikov, Ivan V.,Gusevskaya, Elena V.
, (2019/08/02)
Terpenes are an abundant class of natural products, which is important for flavor and fragrance industry. Many acid catalyzed reactions used for upgrading terpenes still involve mineral acids as homogeneous catalysts and/or toxic solvents. Heteropoly acids represent a well-established eco-friendly alternative to conventional acid catalysts. As these reactions are usually performed in the liquid phase, solvents play a critical role for the process sustainability. In the present work, we developed a catalytic route to valuable fragrance ingredients, dihydrocarvone and carvenone, from limonene oxide by its isomerization using silica-supported tungstophosphoric acid as a heterogeneous catalyst and dialkylcarbonates as green solvents. The reaction pathway can be switched between dihydrocarvone and carvenone (obtained in 90% yield each) simply by changing the reaction temperature. In addition, we developed an efficient method for kinetic separation of trans-limonene oxide from commercial cis/trans-limonene oxide mixture and stereoselective synthesis of trans-dihydrocarvone.
