Thin films derived from giant, tripod-shaped oligophenylenes end-capped with triallylsilyl groups on hydrogen-terminated Si(111) surfaces

Monolayers of giant, tripod-shaped molecules 1 with each tripod leg composed of seven phenylene units end-capped with a triallylsilyl group were prepared on hydrogen-terminated silicon surfaces (H-Si(111)) via thermally induced surface hydrosilylation. The films were characterized by ellipsometry, contact-angle goniometry, and X-ray photoelectron spectroscopy (XPS). The measured ellipsometric thickness of 24 Angstrom of the films suggests anchoring of 1 on the substrate surface with a tripod orientation of high coverage. By measuring the contact angle hysteresis of a series of probe liquids with systematically varied sizes, the molecular pores present on the films consisting of the intercalated molecules of 1 are similar to the cross sectional areas of glycerol and decalin of 0.32-0.49 nm(2). Finally, as evidenced by XPS, excellent yields ( approximately 90%) of Suzuki coupling reactions with arylboronic acid derivatives on the films was achieved, suggesting that the desired tripod orientation of such giant molecules as 1 helps to eliminate the steric hindrance for the reaction.     

An efficient convergent synthesis of adenosine-5′-N-alkyluronamides

Herein we report an efficient synthesis of adenosine-5′-N-alkyluronamides in which an enzyme-mediated deacetylation reaction is a key to the selective modification of the 5′-N-position, prior to coupling the ribose and purine components via a microwave-assisted Vorbrüggen coupling. This approach provides access to highly functionalised adenosines with 2- and N⁶-substitutents, which can be incorporated before or after the ribose-coupling step. In all cases the microwave-assisted Vorbrüggen coupling conditions afforded anomerically pure purine ribosides in good to excellent yields.     

An efficient approach towards the convergent synthesis of "fully-carbohydrate" mannodendrimers

Glycosylation of sugar trityl ethers with sugar 1,2-O-(1-cyano)ethylidene derivatives (the trityl-cyanoethylidene condensation) has been applied to the synthesis of highly branched (dendritic) mannooligosaccharides incorporating a Manalpha1-->3(Manalpha1-->6)Man structural motif. The convergent synthetic strategy used to assemble these oligosaccharides was based on the use of glycosyl acceptors and/or a glycosyl donor already bearing this structural motif. The former were represented by mono- and ditrityl ethers of ManalphaOMe, Manalpha1-->3ManalphaOMe, and Manalpha1-->3(Manalpha1-->6)ManalphaX, where X=OMe or SEt. The pivotal glycosyl donor was the peracetylated 1,2-O-(1-cyano)ethylidene-3,6-di-O-(alpha-D-mannopyranosyl)-beta-D-mannopyranose (1), prepared by orthogonal Helferich glycosylation of the known 1,2-O-(1-cyano)ethylidene-beta-D-mannopyranose with tetra-O-acetyl-alpha-D-mannopyranosyl bromide followed by O-acetylation. Glycosylation of acetates of methyl 6-O-trityl-alpha-D-mannopyranoside and methyl 3,6-di-O-trityl-alpha-D-mannopyranoside with one equivalent of the donor 1 gave rise to the isomeric tetrasaccharide derivatives, Manalpha1-->3(Manalpha1-->6)Manalpha1-->6ManalphaOMe and Manalpha1-->3(Manalpha1-->6)Manalpha1-->3ManalphaOMe, respectively. The latter derivative was further mannosylated at the remaining 6-O-trityl acceptor site to give the protected pentasaccharide Manalpha1-->3(Manalpha1-->6)Manalpha1-->3(Manalpha1-->6)ManalphaOMe. The isomeric pentasaccharide, Manalpha1-->3(Manalpha1-->6)Manalpha1-->6(Manalpha1-->3)ManalphaOMe, was prepared by reaction of 1 with the 6-O-trityl derivative of (Manalpha1-->3)ManalphaOMe. In a similar fashion, 6'- and 6"-O-trityl derivatives of the branched trisaccharide Manalpha1-->3(Manalpha1-->6)ManalphaOMe served as precursors for two isomeric mannohexaosides. The 3,6-di-O-trityl ether of ManalphaOMe and the 6',6"-di-O-trityl ether of Manalpha1-->3(Manalpha1-->6)ManalphaX (X=OMe or SEt) were efficiently bis-glycosylated with the donor 1 to give the corresponding protected mannoheptaoside and mannononaoside. The yields of these glycosylations with the donor 1 ranged from 50 to 66 %. Final deprotection of all the oligosaccharides was straightforward and afforded the target products in high yields. Both the acylated and deprotected products were characterized, and the intersaccharide connectivities were elucidated by extensive one- and two-dimensional NMR spectroscopy. The described blockwise convergent approach allows assembly of a variety of 3,6-branched mannooligosaccharides.     

An efficient synthesis of novel l-rhamnose based non-ionic surfactants under controlled microwave irradiation

The scope and limitations of microwave-assisted glycosylation for the preparation of various alkyl l-rhamnoside amphiphiles were investigated. Straightforward coupling of hydrophilic unprotected sugar and hydrophobic high molecular weight alcohols, in the presence of p-toluenesulfonic acid as a promoter, yielded structurally different compounds in very good yields (37–87%). A homologous series including 17 examples of alkyl α-l-rhamnoside amphiphiles varying in chain structure (C₄–C₂₀) is reported. The structures of the new derivatives were determined by NMR spectroscopy and quantum chemical calculations. Molecular geometry optimizations of different ring forms (¹C₄ and ⁴C₁) and anomeric configurations were carried out using DFT calculations. Herein we demonstrate the advantages of microwave irradiation for the preparation of a broad variety of linear and branched-chain alkyl α-l-rhamnosides. The application of this approach to the synthesis of new natural non-ionic surfactants makes this method attractive because of their potential use in biomedical and pharmaceutical chemistry.     

An effcient and facile synthesis of novel 1,2,3-triazolyl-N- acylpyrazoline hybrids简

An efficient and facile synthesis of a library of hitherto novel 1,2,3-triazolyl-N-acetyl/N-propionylpyrazoline hybrids(16 examples) in excellent yields(90%–96%) has been accomplished from easily accessible 1,2,3-triazolyl chalcone precursors.     

An efficient synthesis of novel 2,4-disubstituted tetrahydroquinolines and quinolines

A series of novel tetrahydroquinolines have been synthesized via the acid-catalyzed reaction of an azaflavan-4-ol with a variety of reactive nucleophiles. The tetrahydroquinolines were found to undergo oxidation in the presence of iodine as catalyst to generate the corresponding novel 2,4-disubstituted quinolines.     

An efficient synthesis and reactions of novel indolylpyridazinone derivatives with expected biological activity

Reaction of 4-anthracen-9-yl-4-oxo-but-2-enoic acid (1) with indole gave the corresponding butanoic acid 2. Cyclocondensation of 2 with hydrazine hydrate, phenyl hydrazine, semicarbazide and thiosemicarbazide gave the pyridazinone derivatives 3a-d. Reaction of 3a with POCl(3) for 30 min gave the chloropyridazine derivative 4a, which was used to prepare the corresponding carbohydrate hydrazone derivatives 5a-d. Reaction of chloropyridazine 4a with some aliphatic or aromatic amines and anthranilic acid gave 6a-f and 7, respectively. When the reaction of the pyridazinone derivative 3a with POCl(3) was carried out for 3 hr an unexpected product 4b was obtained. The structure of 4b was confirmed by its reaction with hydrazine hydrate to give hydrazopyridazine derivative 9, which reacted in turn with acetyl acetone to afford 10. Reaction of 4b with methylamine gave 11, which reacted with methyl iodide to give the trimethylammonium iodide derivative 12. The pyridazinone 3a also reacted with benzene- or 4-toluenesulphonyl chloride to give 13a-b and with aliphatic or aromatic aldehydes to give 14a-g. All proposed structures were supported by IR, (1)H-NMR, (13)C-NMR, and MS spectroscopic data. Some of the new products showed antibacterial activity.     

An expeditious and convergent synthesis of ailanthoidol

An expeditious and concise method has been described for the synthesis of ailanthoidol through convergent route starting from vanillin. The protocol involving intramolecular Wittig as a key reaction afforded ailanthoidol in overall high yield.     

An efficient synthesis of chalcones based on the Suzuki reaction

A general method for the synthesis of chalcones based on the Suzuki reaction either between cinnamoyl chlorides and phenylboronic acids or between benzoyl chlorides and phenylvinylboronic acids is described.     

A novel, stereoselective and convergent synthesis of aryltetralins

A novel one-pot, two-component condensation reaction between readily available allylsiloxanes and electron-rich aldehydes generates aryltetralins with complete control of stereochemistry.     

An efficient synthesis of novel heterocyclic systems incorporating coumarin moiety

Polyfunctional 3-chloro-3-(4-chlorocoumarin-3-yl)prop-2-enal ( 1 ) used as a precursor for heterocyclic synthesis. Dichloro-aldehyde 1 was allowed to react with variable nucleophilic reagents, and a diversity of heterocyclic systems linked coumarin moiety at position 3 was synthesized. The reaction of compound 1 with guanidine and cyanoguanidine produced 3-(pyrimidin-4-yl)-4-chlorocoumarins 2 and 3 . Treating compound 1 with 3-amino-1,2,4-triazole and 2-aminobenzimidazole yielded triazolo[4,3-a]pyrimidine 4 and pyrimido[1,2-a]benzimidazole 5 . The treatment of compound 1 with cyanoacetamide, N-benzyl-2-cyanoacetamide, and 1H-benzimidazolylacetonitrile gave 2(1H)-pyridones 6 , 7 and pyrido[1,2-a]benzimidazole 8 . The reaction of compound 1 with 5-amino-3-methyl-1H-pyrazole and 6-aminouracil afforded pyrazolo[3,4-b]pyridine 9 and pyrido[2,3-d]pyrimidine 10 , respectively. Compound 1 reacted with ethylenediamine, o-phenylenediamine , o-aminophenol, and o-aminothiophenol leading to 5-(imidazolylmethyl)chromeno[4,3-e] [1,4]diazepine ( 12 ), 3-(benzodiazepin/benzoxazepin-2-yl)-4-chlorocoumarins 13 , 14 , and 6-(benzothiazol-2-ylmethyl)chromeno[4,3-b][1,5]benzothiazepine 16 , respectively. Structures of the new synthesized products were deduced on the basis of their analytical and spectral data.     

An efficient one-pot synthesis of novel 4-aryl-1-methyloxindoles

An unprecedented synthetic approach to novel 4-aryl-1-methyloxindoles is described. The method involves the intramolecular palladium-catalyzed amidation of N-methyl-2,6-dibromophenylacetamide followed by an in situ Suzuki cross-coupling reaction with a (hetero)arylboronic acid in a one-pot reaction.     

An efficient three-component protocol for the synthesis of novel spiro-oxazinobarbiturates

Some novel spiro-oxazinobarbiturate derivatives have been successfully synthesized in a one-pot, three-component cascade reaction from various azines (pyridine, isoquinoline, quinoline and phenanthridine), 1,3-dimethylalloxan, and several activated acetylenes (alkyl propiolates, dialkyl acetylenedicarboxylates, and butyne-2-one). The high bond forming efficiency (formation of new C-N, C-C, and C-O bonds) of this reaction makes it attractive for the synthesis of spiro-oxazinobarbiturates in a single operation.     

An efficient synthesis of novel deoxy phospha sugar pyrimidine nucleosides

An efficient method is described in the synthesis of several novel deoxy phospha sugar pyrimidine nucleosides in racemic form, analogs of normal sugar nucleosides, in high yields by treatment of (±)-2-aminophospholane 1-oxide with several, α-cyano-, -acetyl-, -ethoxycarbonyl-β-ethoxy-N-ethoxycarbonylacrylamides.     

An efficient synthesis of novel carbocyclic nucleosides with use of ring-closing metathesis from D-lactose

This paper describes an efficient synthetic route for various types of novel carbocyclic nucleosides. The required stereochemistry of the targeted nucleosides was successfully obtained with use of Grubbs cyclization and Trost allylic alkylation from the carbohydrate chiral template "D-lactose".     

An efficient and convergent synthesis of the potent and selective H3 antagonist ABT-239

An efficient and convergent process for the preparation of a potent and selective H₃ receptor antagonist, ABT-239, 1A was accomplished with an overall yield of 64%. The key step in the synthesis is a Sonogashira coupling/cyclization reaction of 1-but-3-ynyl-2-(R)-methylpyrrolidine (9) with 4′-hydroxy-3′-iodo-biphenyl-4-carbonitrile (3). Additionally, the key amine component 2-(R)-methylpyrrolidine (7) was effectively synthesized from the readily available Boc-l-prolinol with a simple catalytical hydrogenolysis as the key step. This column chromatography-free process is highlighted by several simple work-up and purification procedures and is amendable to the large-scale preparation of 1A.     

An efficient one-pot synthesis of novel polysubstituted 4-amino-2,3-dihydropyridines

A convenient and efficient one-pot multi-component synthesis of novel polysubstituted 4-amino-2,3-dihydropyridines from carbonyl compounds, malononitrile and acetonitrile, using indium triflate is reported. Acetonitrile acts both as a solvent as well as a substrate.     

An efficient one-pot synthesis of strongly fluorescent (hetero)arenes polysubstituted with amino and cyano groups

An efficient one-pot synthesis simultaneously results in three types of densely substituted mono-, di- and tetracyclic π-systems, which can easily be isolated. Each chromophore presents a strong fluorescence emission, either in the red, green or blue part of the spectrum.