Phosphorylated,Silylated, and Stannylated Derivatives of α-Mercaptocarbonyl Compounds

The authors are summing up their research in the field of phosphorylation, silylation, and stannylation of -mercaptocarbonyl compounds. Synthetic methods were developed for a series of new saturated and unsaturated organosilicon(tin) reagents that were applied to organophosphorus syntheses. Representatives of new classes of heterocyclic compounds were prepared: 1,3,2-oxathiaphospholenes with four- and five-coordinate phosphorus. A new thiophosphite-thiophosphate rearrangement initiated by molecular oxygen was discovered.     

Stereocontrolled Synthesis of 6′-Deoxy-6′-Fluoro Derivatives of Methyl α-Sophoroside, α-Laminaribioside, α-Kojibioside and α-Nigeroside

Abstract

Sequential tritylation, benzoylation and detritylation of D-glucose, followed by resolution of the crude product by chromatograpEy gave crystalline 1,2,3,4-tetra-O-benzoyl-α- (1) and β-D-glucopyranose (2). Compound 1, 2, and the corresponding methyl α-glycoside 5 were treated with dimethylaminosulfur trifluoride (methyl DAST) to give, respectively, the 6-deoxy-6-fluoro derivatives 3, 4, and 6. Crystalline 2,3,4-tri-O-benzoyl-6-deoxy-6-fluoro-α-D-glucopyranosyl chloride (10) could be obtained from either 3, 4, or 5 by reaction with dichloromethyl methyl ether in the presence of anhydrous zinc chloride. Silver trifluoromethanesulfonate-promoted reaction of 10 with methyl 2-O-(9) and 3-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside (8) gave the corresponding, (β-linked disaccharidës in high yield. Subsequent deprotection afforded the 6′-deoxy-6′-fluoro derivatives of methyl α-sophoroside (13) and methyl 6′ -deoxy-o′-fluoro-α-laminaribioside (16). Condensation of 8 and 9 with 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-glucopyranosyl chloride in the presence of silver perchlorate was highly stereoselective and produced the α-linked disaccharidës 17 and 21, respectively, in excellent yield. Deacetylation of 17 and 21, followed by fluorination of the resulting alcohols 18 and 22 with methyl DAST and subsequent hydrogenolysis, gave 6′-deoxy-6′-fluoro derivatives of methyl α-kojibioside and methyl α-nigeroside 20 and 24, respectively.     

Synthesis of 5,5′-Dialkyl-6,6′-dichloro-2, 2′-bipyridines

5,5′-Dialkyl-6,6′-dichloro-2,2′-bipyridines were synthesized starting from 3-substituted 2-chloro-6-iodopyridines using Pd-catalyzed coupling conditions. 6-Alkyl-3,5-dichloro-2H-1,4-oxazin-2-ones were excellent precursors for the synthesis of these functionalized 2-iodo-6-chloropyridines.     

New Organic Derivatives of O,O′-(o-, m-, and p-Ditolyl)/Dibenzyldithiophosphates: Synthesis and Characterization

Reactions of (m- and p-ClC ₆ H ₄ NH ₂ ), (p-BrC ₆ H ₄ NO ₂ ), and (p-ClCOC ₆ H ₄ NO ₂ ) with sodium O,O′-ditolyl/dibenzylphosphorodithionates, (ArO) ₂ PS ₂ Na, (Ar = o?, m?, and p?CH ₃ C ₆ H ₄ or –C ₆ H ₅ CH ₂ ) in 1:1 molar ratio in refluxing toluene under anhydrous conditions resulted in the formation of the compounds (ArO) ₂ PS ₂ C ₆ H ₄ L and (ArO) ₂ PS ₂ COC ₆ H ₄ L (L = NH ₂ or NO ₂ ) in 87–94% yield. These viscous compounds were characterized by elemental analyses, molecular weight determination, and IR and NMR ( ¹ H, ¹³ C, and ³¹ P) spectroscopic studies, which revealed a monodentate mode of bonding of the dithiophosphate moiety with the carbon of the phenyl ring of the organic moiety leading to a P–S–C linkage.     

Synthesis of cobalt and nickel 6,6′-diphenylbis(dicarbollides)

Russian Chemical Bulletin - 6,6′-Diphenyl derivatives of cobalt and nickel bis(dicarbollide) were synthesized starting from nido-carborane by the insertion—deboronation—insertion...     

New Approaches to the Synthesis of 2,2′: 6′,2″-Terpyridine and Some of Its Derivatives

A new two-step procedure has been developed for the synthesis of 2,2′: 6′,2″-terpyridine and 4′-methylsulfanyl-2,2′: 6′,2″-terpyridine in more than 70% yield on the basis of Potts’ condensation. Efficient methods have been proposed for purification of all condensation products.     

Synthesis of Novel Phosphorylated Daidzein Derivatives and ESI Investigation on Their Non-Covalent Complexes with Lysozyme

Daidzein （7,4＇-dihydroxyisoflavone） was phosphorylated by a modified Atherton-Todd reaction. The structures of the five target product, were determined by X-ray, IR, NMR and ESI-MS. Electrospray ionization results show that in the gas phase all the phosphorylated daidzein derivatives could form non-covalent complexes with the protein lysozyme, while non-covalent complexes were not detected in the mixed solution of daidzein with lysozyme. Relative affinity of every non-covalent complex was obtained according to its different decomposition orifice voltage.     

Synthesis,Spectral Characterization,and Antimicrobial Evaluation of N,N′-(1,4-Phenylene)diurea Derivatives

Russian Journal of Organic Chemistry - A series of new 1,1′-(1,4-phenylene)diurea derivatives were synthesized by reacting 1,4-diiso­cyanato­benzene with various biologically...     

Synthesis of Polyiodides of N- and S-S-Acetonyl Derivatives of 2,2′-(Disulfanediyl)- and 2,2′-[Alkanediylbis(sulfanyl)]-bisbenzimidazolium

Russian Journal of Organic Chemistry - 2,2′-(Disulfanediyl)- and 2,2′-[alkanediylbis(sulfanyl)]-bisbenzimidazoles react with aliphatic, aromatic, and heterocyclic α-iodoketones in...     

Synthesis and Properties of Phosphorylated and Silylated α-Mercaptocarbonyl Compounds

Abstract

Phosphorylation and silylation of α -mercaptooarbonyl compounds have been investigated. A novel type of 1.4 S-O migration trimethylsilyl and P(III) groups has been discovered. The thiophosphite-thiophosphonate rearrangement when exposed to oxygen as well as heterocyclization with the formation of 1,3,2-oxathiaphospholenes and 1,3,2-oxathiasilalenes were also found. Some regularities of these processes and the properties of heterocycles synthesized have also been brought out.     

Synthesis of some new Spiro(Pyran-4,2′- Oxazolidine) and Pyridoxazolidine Derivatives

Ketene S,S-acetal 2 reacts with aminoethanol to afford 2-(1-acetal -2-oxo propylldine)oxazolldine 3 which was allowed to react with some active methylene compounds having an α- cyano or α-keto group to give spiro(pyran -4,2′-oxazolldine) derivatives 6-11. Compound 3 reacted with some α, β -unsaturated nltriles to afford the corresponding pyrldoxazolldine derivatives 12a-h through a nucleophillc addition and cyclization.     

Synthesis and Luminescence Spectral Properties of New Cyano-Substituted 2,2′-Bipyridine Derivatives

Russian Journal of Organic Chemistry - Previously unknown 2-{4-aryl-5-cyano-[2,2′-bipyridin]-6(1H)-ylidene}malononitriles were synthe­sized by reaction of...     

One-Pot Synthesis of 5′-Diaryl Esters and Diamidates of Phosphate,Phosphorothioate, and Phosphoroselenoate Derivatives of AZT and d4T

Modified nucleosides such as 3′-azido-2′,3′-dideoxythymide (AZT) and 2′,3′-dideoxy-2′,3′-didehydrothymide (d4T) are of importance as antiviral agents and in other medicinal applications. Consequently, there is interest in new analogs of these compounds and in new methods for preparing them. In this article, a simple but efficient, one-pot synthesis of 5′-diaryl esters and diamidates of phosphate, phosphorothioate, and phosphoroselenoate derivatives of AZT and d4T is described. The reaction of AZT/d4T with phosphorus trichloride, followed with phenols, aniline, or amino acid methyl esters in the presence of a base, led to the corresponding tricoordinated phosphite compounds of AZT/d4T, which were then oxidized with 3-chloroperoxybenzoic acid (m-CPBA), sulfur, or selenium powder to finally afford the corresponding target compounds in good yield.     

Synthesis and Characterization of Picolinamide Calix[6]arenes Derivatives

It is well known that calixarenes are extremely versatile classes of macrocyclic receptor able to complex various metal ions as well as to selectively recognize both neutral and charged inorganic or organic species in solution. It is unable to get a clear…     

Synthesis and Structure Elucidation of Celangulin Derivatives

Celangulins are sesquiterpene polyol esters based on a core structure known as β-dihydroagarofuran from Celastrus angulatus Max. Some of them are environment acceptable-pesticides. In order to find new active compounds and study their SAR, sesquiterpene polyol esters libraries were synthesized based on the basic hydrolysis of the extract of the root bark of Celastrus angulatus which could offer the β-dihydroagarofuran polyol by combinatorial chemical method and the compounds with insecticidal activity were isolated by bioassay-guided fractionation. Two new compounds with insecticidal activity against Mythimna separata, were isolated and elucidated as 2β,6α,8β, 13-tetraisobutanoyloxy-1β,4,9α-trihydroxy-β-dihydroagarofuran (A) and 1β,2β,6α,8β, 13-pentaisobutanoyloxy-4α,9α-dihydroxy-β-dihydroagarofuran (B) mainly by 1H NMR, 13C NMRH-HCOSY, HMQC, HMBC and HRMS spectral data. A: [α]20D -7.3 (c 0.12, CHCl3), B: [α]20D -34.6 (c 0.8,CHCl3).     

Synthesis and Crystal Structure of Isosteviol Derivatives

Isosteviol (ent-16-ketobeyeran-19-oic acid, I) is a tetracyclic diterpenoid with a beyerane skeleton obtained by acid hydrolysis of stevioside.1 Several tetracyclic diterpenoids, specially the kaurenes, have important biological activities. Recent studies on the microbial transformation of isosteviol have revealed that it is metabolized by Cunninghamella bainieri, Actinoplanes sp., Mucor recurvatus, and Cunninghamella blackesleeana to yield five new metabolites.2 The hydroxylation pattern of…     

Design,Synthesis and Antifungal Activity of Novel Triazole Derivatives

Twenty-one 1-(1H-1,2,4-triazolyl)-2-(2,4-diflurophenyl)-3-(4-substituted-1-piperazinyl)-2-propanol derivatives were designed and synthesized,on the basis of the active site of lanosterol 14α-demethylase.In vitro antifungal activities showed that some of the target compounds had higher antifungal activity and broader antifungal spectrum than fluconazole.     

Synthesis of Chiral Phenolic 1,1′-Binaphthocrown Ethers and Some Proton-ionisable Chromogenic Derivatives

Synthesis of mono- and bis(1,1′-bi-2-naphthocrown)ethers containing bis(2,6-methylene)anisyl subunit in the crown ring were developed. These chiral macrocycles are suitable precursors to introduce a chromogenic function, as exemplified by two novel crowned azophenol chromoionophores. Their coloration process induced by various achiral and chiral amines was studied by UV–vis spectrophotometry.