Impact of the Carbene Derivative Charge on the Decomposition Rates of Hoveyda-Grubbs-like Metathesis Catalysts.

Hoveyda-Grubbs metathesis catalysts undergo a relatively fast decomposition in the presence of olefins. Using a computational density functional theory approach, we show that positively charged derivatives of N-heterocyclic carbenes have little impact on the degradation/deactivation rates of such catalysts with respect to neutral carbenes. On the other hand, the hypothetical anionic Hoveyda-Grubbs-like catalysts are predicted to less likely undergo degradation in the presence of the olefin, while being as active as standard, neutral Hoveyda-Grubbs catalysts.

Impact of the olefin structure on the catalytic cycle and decomposition rates of Hoveyda-Grubbs metathesis catalysts.

A relatively fast degradation of ruthenium catalysts in the presence of selected olefins, and ethylene in particular, is one of the bottlenecks in their use in metathesis reactions. Here we explore the structure-activity relationships between the rate of degradation of Hoveyda-Grubbs catalysts and the structure of olefins by means of DFT calculations. We show that (Z)-1,2-dichloroethene can't form stable complexes with a 14-electron active complex due to a strong inductive electron withdrawal effect. Hoveyda-Grubbs catalysts can be, however, used to convert (Z)-1,2-dichloroethene to (E)-1,2-dichloroethene due to differences in crucial barriers in the catalytic cycle for E/Z isomers. Hoveyda-Grubbs catalysts in the presence of both isomers of 1,2-dimethoxyethene and 1,2-dichloroethene are predicted to be very stable in the unproductive metathesis, while for monosubstituted olefins the methoxyethene presence gives relatively low barriers for crucial degradation transition states and can readily undergo decomposition.

α-Photooxygenation of chiral aldehydes with singlet oxygen.

Organocatalytic α-oxygenation of chiral aldehydes with photochemically generated singlet oxygen allows synthesizing chiral 3-substituted 1,2-diols. Stereochemical results indicate that the reaction in the presence of diarylprolinol silyl ethers is highly diastereoselective and that the configuration of a newly created stereocenter at the α-position depends predominantly on the catalyst structure. The absolute configuration of chiral 1,2-diols has been unambiguously established based on electronic circular dichroism (ECD) and TD-DFT methods.

The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study.

Cationic carbenes are a relatively new and rare group of ancillary ligands, which have shown their superior activity in a number of challenging catalytic reactions. In ruthenium-based metathesis catalysis they are often used as ammonium tags, to provide water-soluble, environment-friendly catalysts. In this work we performed computational studies on three cationic carbenes with the formal positive charge located at different distances from the carbene carbon. We show that the predicted initiation rates of Grubbs, indenylidene, and Hoveyda-Grubbs-like complexes incorporating these carbenes show little variance and are similar to initiation rates of standard Grubbs, indenylidene, and Hoveyda-Grubbs catalysts. In all investigated cases the partial charge of the carbene carbon atom is similar, resulting in comparable Ccarbene-Ru bond strengths and Ru-P/O dissociation Gibbs free energies.

The Vibrational Circular Dichroism Pattern of the ν(C=O) Bands in Isoindolinones.

The IR and vibrational circular dichroism (VCD) spectra of both enantiomers of Me-, iPr-, nBu-, Ph-, and CH2 Ph-substituted isoindolinones in solution and KBr pellets were measured and interpreted by DFT calculations. The spectra in solution revealed no important differences in the C=O stretching vibration region while the interpretation of very distinct spectra taken in pellets required determining the crystal structures. The studied compounds crystallized in the P21 21 21 (Me, iPr, CH2 Ph), P31 (nBu), and P21 (Ph) space groups. We found that the quality of simulated spectra strongly depends on the substituent, the structure of the molecular cluster assumed, basis set, and use of the dispersion correction. The IR spectra can be reproduced well based on the simplest linear arrangement of hydrogen-bonded chains mimicking the molecular arrangement in the crystals. We found no common approach to reproduce all the registered VCD spectra in the crystal phase. For the Me and nBu isoindolinones, the VCD pattern was the best reproduced by full optimization of the selected large molecular clusters. For iPr, Ph and CH2 Ph derivatives optimizing only the position of H-atoms in a fragment frozen as in the crystal provides the best results. Such an approach can reduce the computation time from months to one week.

Synthesis of a sucrose dimer with enone tether; a study on its functionalization.

The reaction of appropriately functionalized sucrose phosphonate with sucrose aldehyde afforded a dimer composed of two sucrose units connected via their C6-positions ('the glucose ends'). The carbonyl group in this product (enone) was stereoselectively reduced with zinc borohydride and the double bond (after protection of the allylic alcohol formed after reduction) was oxidized with osmium tetroxide to a diol. Absolute configurations of the allylic alcohol as well as the diol were determined by circular dichroism (CD) spectroscopy using the in situ dimolybdenum methodology.

Amine-catalyzed direct aldol reactions of hydroxy- and dihydroxyacetone: biomimetic synthesis of carbohydrates.

This article presents comprehensive studies on the application of primary, secondary, and tertiary amines as efficient organocatalysts for the de novo synthesis of ketoses and deoxyketoses. Mimicking the actions of aldolase enzymes, the synthesis of selected carbohydrates was accomplished in aqueous media by using proline- and serine-based organocatalysts. The presented methodology also provides direct access to unnatural L-carbohydrates from the (S)-glyceraldehyde precursor. Determination of the absolute configuration of all obtained sugars was feasible using a methodology consisting of concerted ECD and VCD spectroscopy.

Dimolybdenum tetracarboxylates as auxiliary chromophores in chiroptical studies of vic-diols.

The aim of the present work was to check the suitability of dimolybdenum carboxylates, other than commonly used [Mo2(OAc)4], as auxiliary chromophores for determining the absolute configuration of optically active vic-diols by means of electronic circular dichroism (ECD). To this end, a set of dimolybdenum tetracarboxylates was synthesized, and subsequently, the two most promising compounds were selected, namely dimolybdenum tetrakis(µ-pivalate) and tetrakis(µ-isovalerate). The selection was based on their solubility in commonly used solvents, their stability in solution, their tolerance to air exposure, as well as their utility for dichroic studies. The stability of the obtained in situ chiral complexes was verified by measuring the dependence of ECD, UV-vis, and NMR spectra on time, temperature, and concentration. We have shown that the ECD spectra of diverse vic-diols with these complexes are suitable for configurational assignment based on the correlation between signs of Cotton effects (CEs) arising in the spectra and the stereostructure of the ligand. Furthermore, to aid in the interpretation of experimental results, a separate set of DFT calculations has been incorporated to provide additional insight into the structure of the chiral complexes involved. In contrast to the earlier assumptions, experiments showed that the chelating mode of ligation is preferred for the studied complexes.

Ruthenium nitronate complexes as tunable catalysts for olefin metathesis and other transformations.

Novel ruthenium(II) complexes were obtained as a result of a stoichiometric reaction of Grubbs' benzylidene second generation catalysts with 3-nitropropene. These stable complexes, formally ruthenaisoxazole N-oxide derivatives, display activity in both metathesis and non-metathetic processes such as cycloisomerisation, isomerisation and transfer hydrogenation.