We here report a computational approach on the mechanism of allylicamination reactions using allyl-alcohols and amines as the substrates and phosphoramidite palladium catalyst 1a, which operates in the presence of catalytic amount of 1,3-diethylurea as a co-catalyst. DFT calculations showed a cooperative hydrogen-bonding array between the urea moiety and the hydroxyl group of the allyl alcohol,...

MP2/aug-cc-pVDZ and B3LYP/cc-pVDZ calculations of the reactions of CH3SSR (R = H or CH3) with fluoride, hydroxide or allyl anion in the gas-phase were performed to determine the mechanism for both elimination and substitution reactions. The elimination reactions were shown to follow the E2 mechanism. The substitution reactions with hydroxide and fluoride proceed by the addition-elimination mech...

The previously unresolved issue of polymerization of allyl monomers CH2 CHCH2 X is overcome by a palladium-catalyzed insertion polymerization of diallyl ether as a monomer. An enhanced 2,1-insertion of diallyl ether as compared to mono-allyl ether retards the formation of an unreactive five-membered cyclic O-chelate (after 1,2-insertion) that otherwise hinders further polymerization, and also ...

The title compound, [PdBr(C(3)H(5))(C(9)H(8)N(2))], was synthesized by the reaction of the allyl-palladium(II) bromide dimer and 1-phenyl-1H-imidazole. The Pd atom is coordinated by one allyl group [in η(3) mode, the central CH group of the allyl group is disordered over two sets of sites in a 0.668 (5):0.332 (5) ratio], one bromide anion and a 1-phenyl-1H-imidazole ligand. Intra-molecular face...

The A [(2)B1] <--X [(2)A2] band system between 380 and 420 nm was observed in a supersonic jet expansion. The allyl radical was found to dissociate following electronic excitation, releasing a hydrogen atom. Monitoring the appearance of the hydrogen atom photoproduct as a function of the excitation laser wavelength, similar spectral features are observed as in earlier absorption experiments. Ti...

We have discovered a mild, catalytic protocol for the regio- and stereoselective synthesis of trisubstituted allyl diarylphosphonates from the corresponding disubstituted allyl silyl ethers, circumventing the challenges related to the preparation and availability of stereodefined trisubstituted olefins. A closely related arylation reaction was also discovered during the methodology development....

The conformation of alinidine a new and specific bradycardic agent was studied using MNDO method. It has been found that the rotation of both phenyl and imidazoline ring of this compound is restricted. Of two possible isomers of irnidazoline ring, the one with NH in the cis position to allyl side chain is slightly more stable. On the other hand, the allyl group can rotate freely and at leas...

The degradation of PVC at a processing temperature is mostly caused by its abnormal and unsta— ble molecular structures. It has been pointed out that its allyl chloride structures play a significant role as the abnormal and unstable structures. Inasmuch as the allyl chloride struc— tures are markedly more chemically active than the normal structure, the selective chemical treatments are applica...