Yao Fu

Most photoredox catalysts in current use are precious metal complexes or synthetically elaborate organic dyes, the cost of which can impede their application for large-scale industrial processes. We found that a combination of triphenylphosphine and sodium iodide under 456-nanometer irradiation by blue light-emitting diodes can catalyze the alkylation of silyl enol ethers by decarboxylative coupling with redox-active esters in the absence of transition metals. Deaminative alkylation using Katritzky's N-alkylpyridinium salts and trifluoromethylation using Togni's reagent are also demonstrated. Moreover, the phosphine/iodide-based photoredox system catalyzes Minisci-type alkylation of N-heterocycles and can operate in tandem with chiral phosphoric acids to achieve high enantioselectivity in this reaction.

As the main component of lignocelluloses, cellulose is a biopolymer consisting of many glucose units connected through β-1,4-glycosidic bonds. Breakage of the β-1,4-glycosidic bonds by acids leads to the hydrolysis of cellulose polymers, resulting in the sugar molecule glucose or oligosaccharides. Mineral acids, such as HCl and H2SO4, have been used in the hydrolysis of cellulose. However, they suffer from problems of product separation, reactor corrosion, poor catalyst recyclability and the need for treatment of waste effluent. The use of heterogeneous solid acids can solve some of these problems through the ease of product separation and good catalyst recyclability. This review summarizes recent advances in the hydrolysis of cellulose by different types of solid acids, such as sulfonated carbonaceous based acids, polymer based acids and magnetic solid acids. The acid strength, acid site density, adsorption of the substance and micropores of the solid material are all key factors for effective hydrolysis processes. Methods used to promote reaction efficiency such as the pretreatment of cellulose to reduce its crystallinity and the use of ionic liquids or microwave irradiation to improve the reaction rate are also discussed.

Easy access: An unprecedented copper-catalyzed cross-coupling reaction of the title compounds with diboron reagents is described (see scheme; Ts = 4-toluenesulfonyl). This reaction can be used to prepare both primary and secondary alkylboronic esters having diverse structures and functional groups. The resulting products would be difficult to access by other means.

A calibrated B3LYP/6-311++G(2df,2p)//B3LYP/6-31+G(d) method was found to be able to predict the gas-phase adiabatic ionization potentials of 160 structurally unrelated organic molecules with a precision of 0.14 eV. A PCM solvation model was benchmarked that could predict the pK(a)'s of 15 organic acids in acetonitrile with a precision of 1.0 pK(a) unit. Combining the above two methods, we developed a generally applicable protocol that could successfully predict the standard redox potentials of 270 structurally unrelated organic molecules in acetonitrile. The standard deviation of the predictions was 0.17 V. The study demonstrated that computational electrochemistry could become a powerful tool for the organic chemical community. It also confirmed that the continuum solvation theory could correctly predict the solvation energies of organic radicals. Finally, with the help of the newly developed protocol we were able to establish a scale of standard redox potentials for diverse types of organic free radicals for the first time. Knowledge about these redox potentials should be of great value for understanding the numerous electron-transfer reactions in organic and bioorganic chemistry.