To date, water has been poorly studied as the sacrificial electron donor for biocatalytic redox reactions using isolated enzymes. Here we demonstrate that water can also be turned into a sacrificial electron donor to promote biocatalytic redox reactions. The thermodynamic driving force required for water oxidation is obtained from UV and visible light by means of simple titanium dioxide-based photocatalysts. The electrons liberated in this process are delivered to an oxidoreductase by simple flavin redox mediators. Overall, the feasibility of photobiocatalytic, water-driven bioredox reactions is demonstrated.

The development of enantioselective anti-selective Mannich-type reactions of aldehydes and ketones with imines catalyzed by 3-pyrrolidinecarboxylic acid and related pyrrolidine derivatives is reported in detail. Both (3R,5R)-5-methyl-3-pyrrolidinecarboxylic acid and (R)-3-pyrrolidinecarboxylic acid efficiently catalyzed the reactions of aldehydes with alpha-imino esters under mild conditions and afforded anti-Mannich products with high diastereo- and enantioselectivities (anti/syn up to 99:1, up to >99% ee). For the reactions of ketones with alpha-imino esters, (R)-3-pyrrolidinecarboxylic acid was an efficient catalyst (anti/syn up to >99:1, up to 99% ee). Evaluation of a series of pyrrolidine-based catalysts indicated that the acid group at the beta-position of the pyrrolidine ring of the catalyst played an important role in forwarding the carbon-carbon bond formation and in directing anti-selectivity and enantioselectivity.

Not like the others: A molecular palladium oxide cluster was formed by self‐assembly of palladium(II) and arsenic(V) using mild reaction conditions. The resulting heteropolypalladate [PdII13AsV8O34(OH)6]8− has a distorted cubic shape and edge lengths of about 1 nm. The thirteen PdII ions retain four‐coordinate square‐planar geometry, in marked contrast to all other known discrete polyoxometalates.

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We report the development of direct catalytic, enantioselective, anti-selective Mannich-type reactions between unmodified ketones and alpha-imino esters under mild conditions. The reactions were performed using 5-10 mol % of (R)-3-pyrrolidinecarboxylic or (R)-beta-proline as catalyst in an environmentally benign solvent, 2-PrOH, at room temperature. The anti-Mannich products were obtained in good yields with high diastereo- and enantioselectivities (up to anti/syn >99:1, 99% ee). While (3R,5R)-5-methyl-3-pyrrolidinecarboxylic acid is an excellent catalyst for the anti-Mannich-type reactions of aldehydes, it did not efficiently catalyze the corresponding Mannich-type reactions of ketones; (R)-3-pyrrolidinecarboxylic acid did efficiently catalyze the Mannich-type reactions of ketones. (S)-Proline or (S)-2-pyrrolidinecarboxylic acid has been reported to catalyze the Mannich-type reactions of ketones to afford the syn-products. Thus, the position of the carboxylic acid group on the pyrrolidine ring directs the stereoselection of the catalyzed reaction, providing either syn- or anti-Mannich products.

The system Sn-Beta/hydrogen peroxide is applied to the Baeyer±Villiger oxidation of delfone to d-decalactone, which is an industrial fragrance. The reaction is carried out without solvent and with a substrate/catalyst ratio > 200 (wt/wt). Starting with an enantiomerically enriched delfone it is shown that the rearrangement occurs with retention of configuration at the migrating asymmetric carbon atom, and enantiomerically enriched d-decalactone is obtained as product. This process offers clear advantages over the actual industrial production that uses peracids as oxidants.

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A novel heteropolyoxopalladate structural type has been discovered: the polyoxo-15-palladate(II) [Pd(0.4)Na(0.6) subsetPd(15)P(10)O(50)H(6.6)](12-) (Pd(15)) has been prepared in a one-pot self-assembly reaction and characterized by single-crystal XRD, elemental analysis, IR, TGA, (31)P NMR and electrochemistry; preliminary catalytic studies showed that Pd(15) is active as a catalyst in alcohol oxidation by dioxygen.