Excited state proton transfer is not involved in the ultrafast deactivation of Guanine-Cytosine pair in solution.

Different derivatives of Guanine (G) and Cytosine (C), which sterically enforce the Watson-Crick (WC) conformer, have been studied in CHCl(3) by means of broad-band transient absorption spectroscopy. Our experiments rule out the involvement of an Excited State Proton Transfer (ESPT), which dominates the excited state decay of GC in the gas phase. Instead, the ultrafast dynamics via internal conversion occurs in a polar environment mainly by relaxation in the monomer moieties. Time-dependent density functional theory (TD-DFT) calculations in solution indeed indicate that population transfer from the bright excited states toward the charge transfer state is not effective in CHCl(3) and a noticeable energy barrier is associated with the ESPT reaction. ESPT is therefore not expected to be a main deactivation route for GC pairs within DNA.

Asymmetric acid-catalyzed Meerwein-Ponndorf-Verley-Aldol reactions of enolizable aldehydes.

A highly, stereo- and regioselective Meerwein-Ponndorf-Verley-Aldol etherification process of enolizable aldehydes is described. This new transformation is catalyzed by trifluoroacetic acid. The method also allows cross-aldol reactions with alpha-branched enolizable aldehydes and thus provides access to defined configured quaternary stereogenic centers.

Asymmetric histidine-catalyzed cross-aldol reactions of enolizable aldehydes: access to defined configured quaternary stereogenic centers.

A histidine-catalyzed asymmetric direct cross-aldol reaction of enolizable aldehydes is described. In contrast to proline, histidine is able to clearly differentiate the reactivity of various aldehydes. In addition, this approach provides access to syn-configured beta-hydroxyaldehydes. Thus, by application of this new methodology, defined-configuration quaternary stereocenters can be constructed with ease. The utility of this method is demonstrated in several total syntheses of branched-chain carbohydrates.

Total syntheses of carbohydrates: organocatalyzed aldol additions of dihydroxyacetone.

The selective total synthesis of carbohydrates with defined configuration has been of great interest for a long time. This field has been the domain of enzymatic methods so far. But now the recent development of several organocatalyzed aldol methodologies has made a selective synthetic approach to configuratively defined carbohydrates possible. This development and different strategies will be discussed in this concept article.