16603-18-2

A convenient and efficient method was developed for the synthesis of arylacetones from (E)-3-aryl-2-methylacrylic acids through a Curtius rearrangement. The Curtius rearrangement of (E)-3-aryl-2-methylacryloyl azides and subsequent hydrolysis proceeded at mild temperatures in a two-phase medium of carbon tetrachloride and water containing a catalytic amount of tetrabutylammonium bromide to give the corresponding derivatives in 82-93% yield.

An operationally simple and mild one-pot protocol for the synthesis of a variety of 3,5-diarylpyridines from β-nitrostyrenes was achieved by using elemental iron. This reaction proceeds via reduction of the nitro group, resulting in in situ imine formation followed by trimolecular condensation with concomitant debenzylative aromatization. By employing this method, a series of symmetrical and unsymmetrical 3,5-diarylpyridines were synthesized with good to excellent yields. In addition, this method was also utilized for the synthesis of Sch-21418, an anti-inflammatory agent on gram scale.

Mor(DalPhos) for Me(sylates): Described are the first examples of ketone mono-α-arylation and primary aliphatic amine monoarylation employing aryl methanesulfonate coupling partners. A range of functionalized aryl mesylates were employed with dialkyl ketones, and also with primary and secondary amines as well as the otherwise challenging coupling partners acetone and methylamine. Ad=adamantyl. Copyright

Set the ace(tone): A palladium catalyst derived from the bidentate XantPhos ligand and Pd(OAc)2 has enabled broadly applicable mono-α-arylations of acetone to be performed with air- and moisture-stable aryl imidazolylsulfonates as most user-friendly electrophiles (see scheme). Copyright

Fe-HCl mixture was found to selectively perform oxidative hydrolysis of the nitroalkenes 1a-j and nitroalkanes 2a-j to the ketones 3a-j. Also, the reagent was observed to deprotect the oximes 7a-j to carbonyl compounds 8a-j in excellent yields.

1,3-Diarylprop-2-en-1-ones and derivatives, compositions containing them, manufacturing process and use. Substituted 1,3-diarylprop-2-en-1-ones with therapeutic activity may be used in oncology.

The synthesis of (2RS,3RS)-1,4-bis(4-hydroxy-3,5-dimethoxyphenyl)-2,3-dimethylbutan-1-one (9) is described.Diphenolic oxidative coupling of (9) gave the unstable dienone (24), which decomposed in methanol to give what is believed to be the acetal (26).Syn

A series of eight previously undescribed 2,4-diaminothienopyrimidine analogues of the potent dihydrofolate reductase (DHFR) inhibitors trimetrexate (TMQ) and piritrexim (PTX) were synthesized as potential drugs against Pneumocystis carinii and Toxoplasma gondii, which are major causes of severe opportunistic infections in AIDS patients. 2,4-Diamino-5-methyl-6-(aryl/aralkyl)thienopyrimidines with 3,4,5-trimethoxy or 2,5-dimethoxy substitution in the aryl/aralkyl moiety and 2,4-diamino-5-(aryl/aralkyl)thienopyrimidines with 2,5-dimethoxy substitution in the aryl/aralkyl moiety were obtained by reaction of the corresponding 2-amino-3-cyanothiophenes with chloroformamidine hydrochloride.The aryl group in the 5,6-disubstituted analogues was either attached directly to the hetero ring or was separated from it by one or two carbons, whereas the aryl group in the 5-monosubstituted analogues was separated from the hetero ring by two or three carbons. 2-Amino-3-cyano-5-methyl-6-(aryl/alkyl)thiophene intermediates for the preparation of the 5,6-disubstituted analogues were prepared from ω-aryl-2-alkylidenemalononitriles and sulfur in the presence of a secondary amine, and 2-amino-3-cyano-4-(aryl/aralkyl)thiophene intermediates for the preparation of the 5-monosubstituted analogues were obtained from ω-aryl-1-chloro-2-alkylidenemalononitriles and sodium hydrosulfide.Synthetic routes to the heterofore unknown ylidenemalononitriles, and the ketone precursors thereof, were developed.The final products were tested in vitro as inhibitors of DHFR from Pneumocystis carinii, Toxoplasma gondii, rat liver, beef liver, and Lactobacillus casei.A select number of previously known 2,4-diaminothienopyrimidines lacking the 3,4,5-trimethoxyphenyl and 2,5-dimethoxyphenyl substitution pattern of TMQ and PTX, respectively, were also tested for comparison.None of the compounds was as potent as TMQ or PTX, and while some of them showed some selectivity in their binding to Pneumocystis carinii and Toxoplasma gondii versus rat liver DHFR, this effect was not deemed large enough to warrant further preclinical evaluation.

The C-C double bond of a ketene dithioacetal S,S-dioxide was found to undergo reduction with sodium borohydride.This fact provides an efficient synthetic route from an aromatic aldehyde to an alkyl arylmethyl ketone using methylthiomethyl p-totyl sulfone.

-