Alexey V. Salin

Kinetics and Mechanism of Triphenylphosphine Quarternization with Unsaturated Carboxylic Acids in Various Media

Abstract Reactions of tertiary phosphines with unsaturated electrophilic reagents are widely used in synthetic organic chemistry. Typical satellites of these transformations are proton migration processes, which can play decisive role in such reactions. To learn more about proton transfer mechanism, kinetics of reaction of triphenylphosphine with a series of unsaturated carboxylic acids in alcohols, carboxylic acids, and aprotic solvents was studied by spectrophotometry. The form of kinetic equation depends on proton–donor properties of solvent and has a general third order. Proton transfer occurs from the solvent in carboxylic acids; the second molecule of substrate is required in aprotic solvents, and both canals of proton migration take place in alcohols. Existent proton transfer canals are isokinetic, attesting to the invariability of general features of the reaction mechanism independent of proton–donor nature at the last step of the interaction. A stepwise mechanism including initial generation of 1,3-dipole followed by proton transfer to the carbanionic centre from the medium is suggested.

Kinetic Study of the Reaction of Tertiary Phosphines with Acrylic Acid in Aprotic Solvents

Abstract The kinetics of the reaction of tertiary phosphines with acrylic acid in a series of aprotic solvents was studied by spectrophotometry. The data obtained suggest a stepwise mechanism of interaction including initial formation of zwitterionic intermediate followed by intermolecular proton transfer to the generated carbanionic center from the second molecule of acrylic acid.

Efficient hydrophosphorylation of activated alkenes under phosphine catalysis

GRAPHICAL ABSTRACT ABSTRACT Conjugate addition of diisobutyl phosphite to activated alkenes under PBu3 catalysis affords corresponding phosphonates in high yields within short reaction times.

Mechanistic insights into phospha–Michael reaction of tertiary phosphines with electron-deficient alkenes

ABSTRACT The Michael-type addition of tertiary phosphines to electron-deficient alkenes is a convenient way to generate reactive phosphonium zwitterionic intermediates, which participate readily in many synthetically useful transformations. Although the synthetic usefulness of the phospha–Michael addition has been largely demonstrated, knowledge on the kinetics and mechanism of this reaction is sparse. This paper briefly summarizes the contribution of our research group to find out the mechanism of this reaction. GRAPHICAL ABSTRACT

Synthesis of 2-d-acrylamide

2-d-Acrylamide was synthesized via the 2-step procedure starting from acrylonitrile and deuterium oxide. This procedure affords 2-d-acrylamide in 99.9% chemical purity and 98.4% isotopic enrichment.