Kinetics of Electrophilic Alkylations of Barbiturate and Thiobarbiturate Anions.

Second-order rate constants (k2) of the reactions of various barbiturate anions such as the parent barbiturate, 1,3-dimethylbarbiturate, 2-thiobarbiturate, and 1,3-diethyl-2-thiobarbiturate with diarylcarbenium ions and Michael acceptors have been determined in dimethyl sulfoxide solution at 20 °C. The reactivity parameters N and sN of the barbiturate anions were derived from the linear plots of log k2 versus the electrophilicity parameters E of these reference electrophiles, according to the linear-free-energy relationship log k2 (20 °C) = sN (E + N). Several reactions of these nucleophiles with benzylidenemalononitriles and quinone methides proceeded with reversible formation of the new C-C-bond followed by rate-determining proton shift. No evidence for initial attack of the electrophiles at the enolate oxygens of these nucleophiles was found by the kinetic measurements, in line with quantum chemical DFT calculations, which showed that in all cases C-attack is kinetically and thermodynamically preferred over O-attack. The nucleophilic reactivities of barbiturate anions were compared with those of structurally related carbanions, e.g., Meldrum's acid and dimedone anions.

Design, Synthesis, EPR-Studies and Conformational Bias of Novel Spin-Labeled DCC-Analogues for the Highly Regioselective Labeling of Aliphatic and Aromatic Carboxylic Acids.

Novel types of spin-labeled N,N'-dicyclohexylcarbodiimides (DCC) are reported that bear a 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) residue on one side and different aromatic and aliphatic cyclohexyl analogues on the other side of the diimide core. These readily available novel reagents add efficiently to aliphatic and aromatic carboxylic acids, forming two possible spin-labeled amide derivatives with different radical distances of the resulting amide. The addition of aromatic DCC analogues proceeds with excellent selectivity, giving amides where the carboxylic acid is exclusively connected to the aromatic residue, while little or no selectivity was observed for the aliphatic congeners. The usefulness of these adducts in structural studies was demonstrated by EPR (electron paramagnetic resonance) measurements of biradical adducts of biphenyl-4,4'-dicarboxylic acids. These analyses also reveal high degrees of conformational bias for aromatic DCC derivatives, which further underlines the powerfulness of these novel reagents. This observation was further corroborated by quantum chemical calculations, giving a detailed understanding of the structural dynamics, while detailed information on the solid state structure of all novel reagents was obtained by X-ray structure analyses.

Amide-Substituted Titanocenes in Hydrogen-Atom Transfer Catalysis.

Two new catalytic systems for hydrogen-atom transfer (HAT) catalysis involving the N-H bonds of titanocene(III) complexes with pendant amide ligands are reported. In a monometallic system, a bifunctional catalyst for radical generation and reduction through HAT catalysis depending on the coordination of the amide ligand is employed. The pendant amide ligand is used to activate Crabtree's catalyst to yield an efficient bimetallic system for radical generation and HAT catalysis.

Highly Active Titanocene Catalysts for Epoxide Hydrosilylation: Synthesis, Theory, Kinetics, EPR Spectroscopy.

A catalytic system for titanocene-catalyzed epoxide hydrosilylation is described. It features a straightforward preparation of titanocene hydrides that leads to a reaction with low catalyst loading, high yields, and high selectivity of radical reduction. The mechanism was studied by a suite of methods, including kinetic studies, EPR spectroscopy, and computational methods. An unusual resting state leads to the observation of an inverse rate order with respect to the epoxide.

Approaching Phosphorescence Lifetimes in Solution: The Two-Component Polarizable-Embedding Approximate Coupled-Cluster Method.

Theoretical description of phosphorescence lifetimes in the condensed phase requires a method that takes into account both spin-orbit coupling and solvent-solute interactions. To obtain such a method, we have coupled our recently developed two-component coupled-cluster method with singles and approximated doubles to a polarizable environment. With this new method, we investigate how different solvents effect the electronic phosphorescence energies and lifetimes of 4H-pyran-4-thione.

Barbituric acid as a substituent at aryl methylium ions.

Activation of different benzophenone derivatives with triflic anhydride for electrophilic aromatic substitution of 5-phenylbarbituric acids leads to regioselective formation of the ortho-substituted product. The resulting triphenylmethylium salt can be isolated when the Michlers ketone is used. More electrophilic cations form cyclic enol ethers such as 1-n-butyl-9,9-diaryl-1,9-dihydro-10-oxa-1,3-diazaphenanthrene-2,4-diones. Alternatively, supramolecular complex formation with 2,6-diacetamido pyridine as well as carbenium ion generation have been studied. Although in dilute acid only protonation of one of the carbonyl oxygens occurs, ring opening of the cyclic enol ether toward the carbenium ion is observed in 96% sulfuric acid.