T. A. Podrugina

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.

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.

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.

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.

Spectral and kinetic parameters of photoexcited complexes of albumin and indotricarbocyanine dye with phosphonate substituents

315 Complexation of indotricarbocyanine dyes with human serum albumin (HSA) is a principal factor determining the main parameters in the fluorescent identification of biomacromolecules in medical prac tice [1–3]. The efficiency of dyes in these methods is defined by impacts of fluorescence, intersystem cross ing, internal conversion, and photoisomerization [4]. Recently, we established the general regularities of complex formation and degradation of the photoexci tation energy in the complexes of HSA with indotri carbocyanine green (ICG) [5, 6] with two sulfo groups in its structure. These groups provide high solubility of ICG in aqueous solutions. The solubility of fluoro phores in the aqueous solutions can be attained also by introduction of other hydrophilic groups in the struc ture of cyanine dyes. This study deals with experimen tal investigation on complex formation and energy degradation of photoexcited complexes of albumin and the novel synthesized dye of indotricarbocyanine family ICG P with two ether phosphonate groups in the 3,3’ positions at the nitrogen atoms.

Phosphonium-Iodonium Ylides with Heteroatomic Groups in the Synthesis of Annelated P-Containing Heterocycles

The preparation and chemistry of novel sulfonyl- and phosphoryl-derived λ(3)-iodanes are reported. These compounds with three different heteroatoms attached to a negatively charged C atom represent potentially useful reagents that combine in one molecule the synthetic advantages of a phosphonium ylide and an iodonium salt. Specifically, they can react with a number of acetylenes, leading to hitherto unknown sulfonyl- and phosphoryl-substituted phosphinolines, phosphininothiophenes, and a novel type of annelated P-containing heterocycle--phosphininopyrazole.

Synthesis of advanced fluorescent probes — water-soluble symmetrical tricarbocyanines with phosphonate groups

A method for the synthesis of a series of water-soluble heptamethine indocyanine dyes containing a phosphonate group in the substituent bonded to the quaternary nitrogen atom of the indolenine moiety has been developed.