Aryl derivatives natural products carbonylation

Diaryliodonium salts react more or less easily with carbonyl compounds to afford the C-arylated derivatives. Depending upon the nature of the substrate, different experimental conditions have been used. These reactions are generally performed in alcoholic solvents (r-BuOH, r-AmOH.) or in DMF, at temperatures ranging from low (- 78°C) to reflux of the solvent. Arylation of simple ketones has been obtained either by reaction of the ketone enolates with an appropriate diaryliodonium salt, i or by reaction of the ketone enol silyl ether with diaryliodonium fluoride. Phenylation of the potassium enolate of acetone (13) with diphenyliodonium bromide (14) afforded a modest yield of the monophenylation product, but the stimulation with solvated electrons led to overreaction due to the subsequent reaction of the iodobenzene, a good SrnI arylating agent under these conditions. 9... 

Palladium-catalyzed a-arylation of carbonyl derivatives and its applications in the synthesis of natural products 05CJO282. 

Since the discovery of Pd-catalyzed carbonylation of aryl, vinyl, and benzyl halides by Heck in 1974, this reaction has been used for the synthesis of ester, amide, acid, and acid anhydride. We can nse enol triflate, aryl Iriflate, aniUne derivatives, and vinyl silane as the pseudo aryl or vinyl halide. This reaction has now been further extended for the synthesis of aldehyde and ketone by combination with transmetalation. These reactions have widely been used in organic syntheses, especially the syntheses of biologically active substances in the field of fine chemistry and the syntheses of natural products. 

Quinoline derivatives are of wide occurrence in natural products and medicinal drugs they also find applications in polymer chemistry, electronics, and optoelectronics for their excellent mechanical properties as well [200]. The Friedlander synthesis of quinolines is a classic method involving reduction of o-nitro aryl aldehyde as the first step followed by condensation of the reduced product with enolizable carbonyl compound in the presence of a Bronsted or Lewis acid catalyst [201]. To avoid the harsh reaction conditions, the use of ILs has recently gained considerable attention in the synthesis of quinoline derivatives. 

The effects of changes in structure, temperature, and reaction medium on the kinetics of alkaline hydrolysis of aryl esters of phosphinothioic acids (182 R = R = Me or Ph R = Me, R = Ph X = H, Br, Me, or NO2) have been investigated. The effect of the nature of the leaving group on the kinetics of alkaline hydrolysis of aryl diphenylphosphinates has also been reported on. Indirect evidence has been advanced for the participation of the azaphospholi-dines (183) in the solvolysis of A/-[amino(methyl)phosphinyl]-L-phenylalanine derivatives, and it includes the transfer of the P-amino group to the phenyl-alanyl carbonyl. The products from the hydrolysis or ammonolysis of fosfomycin have the threo structure and have been shown to possess no antibiotic activity. ... 

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