E. D. Matveeva

Photochemical Synthesis of Phosphinolines from Phosphonium−Iodonium Ylides

We describe three different series of experiments which were undertaken to test our hypothesis that during irradiation of phosphonium-iodonium ylides (1a, 1b) an electrophilic carbene is generated. By opposing the assumed intermediate to monosubstituted alkynes, we observed in the case of electron-rich substituents at the triple bond a domination of a 1,3-dipolar cycloaddition of the intermediate with the triple bond to yield furans. In the case of electron poorer substituents, the formation of phosphinolines prevails. A second series of experiments was carried out with mixed ylides in which one phenyl ring at the triarylphosphonium group was replaced by a thienyl group. In this case, we observe only an intramolecular reaction with the thienyl ring to yield the phosphinolines 21-23. In a third test, we replaced in the mixed ylides 1a, 1b the COR group by a CN substituent. This modification leads to phosphinolines only and avoids a 1,3-dipolar cycloaddition.

Preparation, structure, and chemistry of phosphorane-derived phenyliodonium sulfonates

Abstract New triphenylphosphorane-derived phenyliodonium triflates and tosylates were prepared by the reaction of the appropriate iodosobenzene sulfonate with stabilized phosphonium ylides. Structure of the triflate derivative was determined by a single-crystal X-ray analysis. These compounds represent a potentially useful class of reagents that combine in one molecule synthetic advantages of a phosphonium ylide and an iodonium salt.

Heterocycles from Phosphonium-Iodonium Ylides. Photochemical Synthesis of λ5-Phosphinolines

A photochemical reaction of mixed phosphonium-iodonium ylides with acetylenes yielding lambda(5)-phosphinolines, a rare class of phosphorus heterocycles hardly accessible by other methods, was found. The yields of lambda(5)-phosphinolines vary from 35% to 80%. The structures of two phosphinolines were established by single-crystal X-ray diffraction. The X-ray diffraction and NMR spectra data indicate the superposition of ylidic and aromatic structures for phosphinolines.

On the mechanism of the Kabachnik-Fields reaction: Does a mechanism of nucleophilic amination of α-hydroxyphosphonates exist?

R2 NH R3 R3–NH2 + + There is a huge literature on this reaction, which considers both preparative aspects [3, 4] and mechanism issues [4–8]. It is obvious that this process is multistage and can involve different intermediates. Overall data on the possible reaction routes are shown in Scheme 2. The complexity of the process also results from the fact that different catalysts are used in this reaction [3], while the initial components (an amine as a base and a hydrophosphoryl compound as an acid) can produce a wide variety of intermediate complexes [4–11].

Ketones in the catalytic three-component one-pot kabachnik : Fields synthesis of α-amino phosphonates

Reactions of carbocyclic, heterocyclic, and steroidal ketones with benzylamine and diethyl phosphite in a catalytic three-component “one-pot” synthesis of α-amino phosphonates were studied. The activities of mono-and binuclear complexes of tetra(tert-butyl)phthalocyanines as catalysts for this process were compared.

Phosphonium-iodonim ylides in nucleophilic substitution reactions

Properties of mixed phosphonium-iodonium ylides were investigated, and the compounds were shown to be capable to behave as O-nucleophiles in nucleophilic substitution reactions.

Synthesis and structure of mixed phosphonium-iodonium ylide

A mixed phosphonium-iodonium ylide, phenyliodoniumethoxycarbonylmethylenetriphenylphosphorane borofluoride, was synthesized. Its structure was established by means of X-ray diffraction analysis. Temperature dependence of 1H, 13C, and 31P spectra of the ylide synthesized was investigated. A dynamic equilibrium between Z and E-isomers was observed.

Hetaryl-Substituted Phosphonium-Iodonium Ylides in Synthesis of Heterocycles

A series of hitherto unknown hetaryl-substituted (in phosphonium part) phosphonium-iodonium ylides were synthesized. The reaction of these mixed phosphonium-iodonium ylides with acetylenes opens a way to new furyl annelated phosphinolines or unusually substituted phosphininofurans.

Three-component catalytic method for synthesis of α-amino phosphonates with the use of α-amino acids as amine component

Interaction of aliphatic and aromatic aldehydes and ketones with optically active L-α-amino acids or their esters in the three-component catalytic one-pot synthesis of α-aminophosphonates was studied. The corresponding α-amino phosphonates are formed in high yields as mixtures of diastereomers.

Triphenylphosphine-2,4,4,6-tetrabromo-2,5-cyclohexadienone complex as a reagent for preparation of carboxylic acid bromides

Triphenylphosphine-2,4,4,6-tetrabromo-2,5-cyclohexadienone complex was successfully used as a new reagent for the synthesis of carboxylic acid bromides which were isolated as individual substances or were identified by conversion into the corresponding anilides. The reaction is chemoselective, and it can be applied to polyfunctional compounds, e.g., hydroxy acids.