Cobalt-catalyzed intramolecular Heck-type reaction of 6-halo-1-hexene derivatives

[reaction: see text] Treatment of 6-iodo-1-hexene derivatives with trimethylsilylmethyl Grignard reagent in the presence of CoCl(2)(dppb) in refluxing THF affords Heck-type products, methylenecyclopentanes, in good yields.     

New efficient total syntheses of derivatives of protoporphyrin-IX bearing deuteriated methyl groups

New total syntheses of hemins which are regioselectively deuteriated in the 1,5 (2), 5 (3) or 8 (4) methyl groups are described. Syntheses of hemins 2 and 3 follow the progression from pyrromethane 12 to t-butyl tripyrrene-carboxylate hydrobromide (17 and 30) and then to a,c-biladiene dihydrobromide (19 and 31), but for reasons of economy in use of labeled monopyrroles, the o,c-biladiene dihydrobromide 40 for hemin 4 is approached in an initially “clockwise” manner by synthesis of a benzyl tripyrrene-carboxylate hydrobromide 37 from the pyrromethane 5. Cyclization of the a,c-biladienes (19, 31, and 40) was accomplished by brief heating in dimethylformamide in the presence of copper(II) chloride.     

New modification of the Prato reaction applied to the synthesis of N-ferrocenylmethylpyrrolidino[60]fullerene

Russian Chemical Bulletin -     

Heck-type reaction of aryldiazonium silica sulfates

Abstract  

Aryldiazonium silica sulfates were employed as new and efficient reagents for Heck-type arylation reactions with styrene and methyl acrylate. The reactions were carried out in an organic solvent, in the presence of Pd(OAc)₂ as precatalyst without use of base and free ligand. The trans isomers of desired products, methyl cinnamates and stilbenes, were obtained with full conversion. Use of a catalytic amount of Pd(OAc)₂ produced the corresponding products in short reaction times and excellent yields.     

Cobalt-catalyzed Heck-type reaction of alkyl halides with styrenes

A cobalt complex, CoCl2[1,6-bis(diphenylphosphino)hexane], catalyzes an alkylation reaction of styrenes in the presence of Me3SiCH2MgCl in ether to yield beta-alkylstyrenes. A variety of alkyl halides including alkyl chlorides can be employed as an alkyl source. A radical mechanism is strongly suggested for this alkylation reaction.     

New approach to the synthesis of fenestrane derivatives

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, p. 2876, December, 1988.     

New approach to the synthesis of deoxynucleoside-phosphoramidite derivatives

A new method for the synthesis of deoxyribonucleoside-phosphoramidite via an intermediate, 5′-0-dimethoxytritylthymidine-3′-0-diisopropylamino-phosphorochloridite, is reported. By using this method, several deoxyribonucleoside phosphoramidite derivatives with different protecting groups at phosphorus including PS and PN bond besides PO bond were synthesized.     

New approaches to the synthesis of organofluorine nitrogenated derivatives

Fluorinated carboxylic acids are valuable building blocks for several types of organofluorine nitrogenated derivatives. In this review paper, several strategies that use these compounds as starting materials are described. First, fluorinated seven-membered cyclic β-amino esters can be diastereoselectively synthesized from these compounds with a ring-closing metathesis (RCM) reaction as the key step. The use of the RCM reaction in a different approach enables the preparation of fluorinated cyclic α-amino acid derivatives. Fluorinated carboxylic acids also constitute the starting material for the asymmetric synthesis of fluorinated allylic amines. Finally, a solution and solid-phase synthesis of fluorinated uracils and thiouracils is described.     

Synthesis of new amphiphilic chlorin derivatives from protoporphyrin-IX dimethyl ester

A simple synthesis of new amphiphilic chlorin derivatives from protoporphyrin-IX dimethyl ester is reported. The preparation of such compounds is based in a straightforward methodology, which involves the Diels-Alder reaction of protoporphyrin-IX dimethyl ester with maleic anhydride followed by addition of nucleophilic species to the initially formed cycloadducts, a transformation, which is highly regioselective. Preliminary photophysical studies with the new compounds show that they meet adequate features for PDT applications.     

The Suzuki reaction applied to the synthesis of novel pyrrolyl and thiophenyl indazoles

The paper describes the Suzuki cross-coupling of a variety of N and C-3 substituted 5-bromoindazoles with N-Boc-2-pyrrole and 2-thiopheneboronic acids. The reactions, performed in the presence of K(2)CO(3), dimethoxyethane and Pd(dppf)Cl(2) as catalyst, gave the corresponding adducts in good yields. The methodology allows the facile production of indazole-based heteroaryl compounds, a unique architectural motif that is ubiquitous in biologically active molecules.     

Palladium-catalyzed Heck-type reaction of 2-chloro acetamides with olefins

Conditions have been developed for the palladium-catalyzed Heck-type reaction of 2-chloro acetamides with several olefins. The regiochemistry of the products obtained speaks in favor of an involvement of palladium enolates in this reaction.     

New synthesis of uracil derivatives

When N,N-dialkylamide dimethylsulfate adducts are reacted with cyanoacetyl urea or carbethoxy acetyl urea, the corresponding dialkylamino alkylidene derivatives are formed which cyclize to substituted uracils in the presence of a strong base. When the adducts of cyclic amides are used, the lactam ring is opened simultaneously on cyclisation.     

New synthesis of 2-heteroarylperfluoropropionic acids derivatives by reaction of azine N-oxides with hexafluoropropene

Hexafluoropropene reacts with aromatic azine N-oxides under mild conditions to produce fluorides of 2-heteroarylperfluoropropionic acids. The reaction proceeds as 1,3-dipolar cycloaddition followed by spontaneous scission of the N--O bond in the isoxazolidine ring and elimination of HF. When the reaction is carried out in the presence of alcohols or N-alkyl anilines, the in situ formed acyl fluorides give the corresponding esters and amides. They can be also treated separately with nucleophiles to produce the respective acylation products, whereas their hydrolysis leads to unstable carboxylic acids that undergo spontaneous decarboxylation to 1-aryl-1,2,2,2-tetrafluoroethanes. This new reaction provides a simple and general method of synthesizing 2-heteroarylperfluoropropionic acid derivatives that were previously unknown and unavailable.     

New "green" approaches to the synthesis of pyrazole derivatives

A novel approach to the synthesis of pyrazole derivatives from tosylhydrazones of alpha,beta-unsaturated carbonyl compounds possessing a beta-hydrogen is proposed, exploiting microwave (MW) activation coupled with solvent free reaction conditions. The cycloaddition was studied on three ketones (trans-4-phenyl-3-buten-2-one, beta-ionone and trans-chalcone). The corresponding 3,5-disubstituted-1H-pyrazoles were obtained in high yields and after short reaction times. In order to simplify and point out the green chemistry features of the method, a further improvement was achieved under the same catalytic conditions with a "one pot" synthesis of these heterocyclic compounds, starting directly from their carbonyl precursors via tosylhydrazones generated in situ. For an exhaustive study, the dielectric properties of the solid reaction mixtures were also measured, in order to obtain input data for the numerical simulation of their heating behaviour in the single mode MW cavity which was used for experimental work. In order to supply a valid methodology and tool for measuring the environmental impact, a comparative study between the synthetic route proposed and the classical synthetic route has been carried out.     

Cascade reaction synthesis of multisubstituted bicyclic pyridone derivatives

An efficient synthesis of novel bicyclic pyridone derivatives via cascade reaction of heterocyclic ketene aminals (HKAs) and 4-arylmethylene-2-phenyloxazol-5(4H)-ones in the presence of acetic acid has been established. Significantly, the protocol affords a straightforward approach to the construction of multisubstituted bicyclic pyridones in which one C–O bond was cleaved and new C–C and C–N bonds were formed in one pot under mild conditions.