Fluorophenyl Bilirubins: Synthesis and Stereochemistry

Summary.  Analogs of bilirubin with vinyl groups replaced by symmetrically-disposed o-fluorophenyls (1, bis-exo, and 2, bis-endo) were synthesized and characterized spectroscopically. Their ¹H NMR spectra and NOE data are consistent with an intramolecularly hydrogen-bonded ridge-tile conformation where each propionic acid group embraces an opposing dipyrrinone. Like bilirubin, 1 and 2 exhibit negative chirality induced circular dichroism (ICD) Cotton effects in chloroform containing quinine. Unlike bilirubin, however, in aqueous buffer containing human serum albumin, 2 exhibits a negative exciton chirality ICD, whereas that of 1 is positive. Received May 22, 2001. Accepted May 29, 2001     

Novel 3-Cyanosubstituted 1,2-Thiaphosphacyclanes: Synthesis and Stereochemistry

The facile synthetic route to 5- and 6-membered 3-cyano-2-oxo-1,2-thiaphosphacyclanes and 6-cyano-2-oxa-10-oxa(thia)-phosphabicyclo [4.4.0]-decane-1-oxides was elaborated via intramolecular S-alkylation in a series of y -haloalkylsubstituted thiophosphorylacetonitriles. The compounds were used to prepare novel P(III)-containing bidentate ligands with definite stereochemistry. Diastereomeric transformations among 2-oxo-1,2-thiaphosphinanes were found and the mechanism of such transformations is suggested.     

Synthesis and Stereochemistry of Exogonic Acid

Exogonic Acid (1) was isolated from the Brazilian tree, Ipomoea operculata. Dahlke and Graf first characterized (1) in 1964. Despite some subsequent work, it was not until 1992 that we determined the absolute stereochemistry of (1) by synthesis of enantiomers of (1) and application of enantioselective gas chromatographic technique. Here we wish to report our new seterocontrolled synthesis of (1) and its methyl ester.     

First Asymmetry Synthesis and Stereochemistry of Glutinone

Rencently, two new sesquiterpenoids, glutinone 1 and lucinone 2, were isolated from the aerial parts of traditional medicine2 Jasonia glutinosa1 by Castillo and co-workers3. However, Castillo only gave the structure of glutinone, but its absolute configuration is still unknown. Here, we wish to report our stereoselective construction of the four possible diastereoisomers (9a, 9b, 9c & 9d) of glutinone. By comparing the spectrum data with that of the natural product, we outlined the stereoc…     

(Hydroxyimino)Phosphonoacetic Acids: Synthesis,Stereochemistry and Reactivity

Abstract

Individual E/Z isomers of the C-methyl ester 1 of α-(hydroxyimino)phosphonoacetic acid (“troika acid”) were recently prepared as dicyclohexylammonium salts and found to be stable at neutral pH.¹ On alkaline demethylation followed by pH adjustment to 6–7, E?1 and Z?1 stereospecifically undergo P-C_αand C_α-C_β cleavage, respectively.¹ Herein we report synthesis of the corresponding P-methyl ester from trimethyl phos-phonoacetate 2. The product was isolated as its bis-DCHA⁺ salt E-3, with stereochemistry assigned by NMR.²     

Synthesis and Stereochemistry of C-Functional Derivatives of Phosphabicyclodecane

Abstract

Methods for synthesis of new phosphabicyclodecanes with substitution in a heterocycle were worked out. Configurations of individual stereoisomers of P (III) phosphabicyclodecanones, their oxides, sulfides and selenides were established by ¹H, ¹³C, ³¹P NMR spectroscopy and X-ray analysis. The results show that electron-acceptor groups (C=O, P=X) enhance mobility of hydrogen atoms in the heterocycle which leads to the increasing ability of phosphabicyclodecanones for deuteration (in a-position to C4, P=X), participation in aminomethylation reaction and to the capability to react with electrophiles. The isomerization of 5-oxo- and 5-hydroxyderivatives of P (IV) phosphahicyclodecane in presence of acid and basic catalysts was detected and studied. The mechanism of ketoenolic and thiophosphoryl-merkaptoilide (selenophosphoryl-selenoloilide) ternary prototropic tautomerism is proposed. By varying the temperature and the nature of the solvent and catalyst, it is possible to alter the direction and depth of isomeric transformations. As the result of the studies of Stereochemical directivity of reactions of nucleophile addition to double C=O and C=C bonds and of electrophile substitution in phosphabicyclodecanones, the functioning possibilities of such compounds were determined. Polyfunctional derivatives of phosphabicyclodecane, which are of interest for fine organic synthesis of new organophosphorus compounds were obtained.     

Synthesis and Stereochemistry of 3-Hydroxy-1,2,3,6-tetrahydropyridines

A series of 1-benzyl-3-hydroxy-1,2,3,6-tetrahydropyridines, multipurpose synthons for fine organic synthesis and potential antiviral compounds, was prepared by the rearrangement of a number of 1-benzyl-3,4- epoxypiperidines under treatment with lithium amides. 3,4-Epoxypiperidines were obtained by oxidation of 1,2,5,6- tetrahydropyridines trifluoroacetates with a trifluoroperacetic acid. Convenient synthetic routes were found and developed. A conformation analysis of the series of stable 3,4-epoxypiperidines and 3-hydroxy-1,2,3,6- tetrahydropyridines was carried out.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 281–287.Original Russian Text Copyright © 2005 by Grishina, Borisenko, Veselov, Petrenko.     

Synthesis and Stereochemistry of New N-Substituted Cytisine Derivatives

A series of new N-substituted cytisine derivatives was synthesized. The ¹ H and ¹³ C NMR spectra of certain compounds exhibit a doubled set of signals. This is explained by formation of diastereomeric pairs in compounds containing an asymmetric center in the substituents. The signal splitting in -COHC=CHCO ₂ H and HC=O (formyl) derivatives is explained by the existence of Z and E invertomers. Their stereochemical features are discussed. Amide conjugation is confirmed by temperature experiments.     

New Six-Coordinate Phosphorus Compounds. Synthesis and Stereochemistry

Abstract

Synthesis and stereochemistry of several new six-coordinate organophosphorus compounds are discussed.     

Synthesis and Stereochemistry of Substituted 1,3-Dioxa-2-silacyclohexanes: VII. Synthesis and Stereochemistry of Substituted 2-Vinyl-2-methyl-1,3-dioxa-2-silacyclohexanes

The stereochemistry of substituted 2-vinyl-2-methyl-1,3-dioxa-2-silacyclohexanes was studied by ^1Hand ^13C NMR spectroscopy. The configurational and conformational assignment of a mixture of 2-vinyl-2,4-dimethyl-1,3-dioxa-2-silacyclohexane diastereomers with various ratios of the cis and trans forms was made. The molecules of both conformers occur chiefly in the chair conformartion with equatorial location of the methyl group at the C⁴ atom. The experimental data were confirmed by AM1 and MM+ optimization of the molecular geometry.     

Synthesis and Stereochemistry of flavan-3,4-diol diacetates

Two hitherto unknown racemates of flavan-3,4-diol diacetate have been prepared and NMR data now available for the complete set of four racemates establish the stereochemistry of these compounds.     

Synthesis and Stereochemistry of Some New 1,3-Oxathiane Derivatives

The synthesis and stereochemistry of some new 2,5-substituted 1,3-oxathiane derivatives are reported. The anancomeric or flexible structure of the derivatives and some peculiar cases of prochirality are revealed by NMR investigations.     

Synthesis and Stereochemistry of Some New Spiro-1,3-perhydrooxazines

Summary.  The synthesis and the stereochemistry of new spiro-1,3-perhydrooxazines are reported. The stereoisomerism of these compounds is discussed considering the data of conformational analysis, the helical chirality of the spiro[5.5]undecane skeleton, and the triligand virtual chiral center belonging to the 1,3-perhydrooxazine ring. Received February 21, 2000. Accepted (revised) April 18, 2000     

Synthesis and Stereochemistry of Some New Spiro-1,3-perhydrooxazines

 The synthesis and the stereochemistry of new spiro-1,3-perhydrooxazines are reported. The stereoisomerism of these compounds is discussed considering the data of conformational analysis, the helical chirality of the spiro[5.5]undecane skeleton, and the triligand virtual chiral center belonging to the 1,3-perhydrooxazine ring.     

Synthesis and Stereochemistry of Some New 1,3-Oxathiane Derivatives

Summary. The synthesis and stereochemistry of some new 2,5-substituted 1,3-oxathiane derivatives are reported. The anancomeric or flexible structure of the derivatives and some peculiar cases of prochirality are revealed by NMR investigations.     

Synthesis and Stereochemistry of Optically Active Selenium and Tellurium Compounds

Abstract

The synthesis and stereochemistry of tricoordinated optically active selenium and tellurium compounds are described. Telluronium salts, telluronium imides, and seleninic acids were prepared and optically resolved by fractional recrystallization of diastereomeric mixtures or by chromatography using a chiral column of racemic mixtures. Diphenyl dichalcogenides also were optically resolved by chiral crystallization. Their absolute configurations were determined or estimated based on X-ray crystallographic analysis, specific rotations, and circular dichroism spectra. The kinetic studies and the mechanism for the racemization were also studied.