Aryl derivatives ketone arylation

Chloro-9-phenylpurine reacts with a variety of nucleophiles including 0-alkyl, 0-aryl, SR, and NHR to produce the 2-substituted purines. The compound also reacts with benzylcyanide and ethyl cyanoacetate to give the corresponding purine-2-CHR(CN) derivative but failed to react with other active methylene derivatives, ketones, or potassium cyanide. In contrast, 9-phenyl-2-methyl-sulfonylpurine reacted readily with active methylene compounds, ketones, and potassium cyanide <87CPB4972>. 

R " = H, alkyl, aryl, substituted alkyl and aryl SIRs = SIMes, SiMe2(t-Bu), SIEts solvent CHoCH. pentane, toluene n = 1-3 chiral oxidant Davis chiral oxaziridine, Shi s D-fructose derived ketone/Oxone, (Salen)manganese(lll)-complexes/NaOCI or PhIO... 

Carbonylation of enol triflates derived from ketones and aldehydes affords Q,/)-unsaturated esters[332]. Steroidal esters are produced via their aryl and enol triflates[328]. The enol triflate in 477 is more reactive than the aryl tritlate and the carbonylation proceeds stepwise. First, carbonylation of the enol triflate affords the amide 478 and then the ester 479 is obtained in DMSO using dppp[333]. 

Superacids such as HF-SbF effect cyclo alkylation of aryl alkyl ketones to give tetralone derivatives (58). Tandem iatramolecular cyclo alkylatioas can be achieved when functional groups are located ia close proximity (59). 

Synthesis and Properties. Polyquinolines are formed by the step-growth polymerization of o-aminophenyl (aryl) ketone monomers and ketone monomers with alpha hydrogens (mosdy acetophenone derivatives). Both AA—BB and AB-type polyquinolines are known as well as a number of copolymers. Polyquinolines have often been prepared by the Friedlander reaction (88), which involves either an acid- or a base-catalyzed condensation of an (9-amino aromatic aldehyde or ketone with a ketomethylene compound, producing quinoline. Surveys of monomers and their syntheses and properties have beenpubhshed (89—91). 

A large variety of newer poly(ether imide)s has been described. Included among these are perfluorinated polymers (96), poly(ester ether imide)s (97), poly(ether imide)s derived from A/,Ar-diamino-l,4,5,8-naphthalenetetracarboxyHcbisimide (98), and poly(arylene ether imide ketone)s (99). In addition, many other heterocyHc groups have been introduced into polyether systems, eg, poly(pyrazole ether)s (100) and poly(aryl ether phenylquinoxaLine)s (101) poly(aryl ether oxazole)s with trifluoromethyl groups (102) and polyethers with other heterolinkages, eg, poly(arylether azine)s (103). 

Another source of C-unsubstituted derivatives are o-aminopyridine aldehydes e.g. 216 - 217) (60JCS1370), and the corresponding ketones may be used to furnish C-aryl compounds (71GEP2051013). 

The photocyclization of N-aryl enamines derived from cyclic or acyclic ketones proceeds under mild conditions to produce 2,3-dihydroindole derivatives (178b). The stereochemistry of the products is predominantly trans, which follows from a photochemical electrocyclic process which should take place in a conrotatory manner (178c,I78d). However, the presence of some cis products is not as easily explained. 

Aldehydes and ketones of furazans and furoxans have many properties resembling those of the aryl derivatives. Reduction of the carbonyl compounds with... 

Quazepam (88) has a highly fluorinated sidechain so as to make this tranquilizer resistant to dealkylation. It also incorporates a lipid-solubilizing 2-thione moiety. The synthesis begins with bi aryl ketone derivative by ] -al kylation with 2,2,2-trifluoroethyltriclate to give 86. 

In general, the rate of syn/anti equilibration increases with decreasing basicity of the enolate and with increasing steric repulsion in the enolate. The first point is illustrated by the fact that aldolates derived from ketones (X = aryl, alkyl) undergo syn/anti equilibration more readily than those derived from amides or carboxylates (X = NR2,0-). It appears that the rate of the retro-aldol addition is higher when the enolate thereby generated is more stable. 

Trialkylboranes react rapidly and in high yields with a-halo ketones,a-halo esters, a-halo nitriles, and a-halo sulfonyl derivatives (sulfones, sulfonic esters, sulfonamides) in the presence of a base to give, respectively, alkylated ketones, esters, nitriles, and sulfonyl derivatives. Potassium tert-butoxide is often a suitable base, but potassium 2,6-di-tert-butylphenoxide at 0°C in THF gives better results in most cases, possibly because the large bulk of the two tert-buXy groups prevents the base from coordinating with the R3B. The trialkylboranes are prepared by treatment of 3 mol of an alkene with 1 mol of BH3 (15-16). With appropriate boranes, the R group transferred to a-halo ketones, nitriles, and esters can be vinylic, or (for a-halo ketones and esters) aryl. " °... 

Aziridines can be prepared directly from double-bond compounds by photolysis or thermolysis of a mixture of the substrate and an azide. The reaction has been carried out with R = aryl, cyano, EtOOC, and RSO2, as well as other groups. The reaction can take place by at least two pathways. In one, the azide is converted to a nitrene, which adds to the double bond in a manner analogous to that of carbene addition (15-62). Reaction of NsONHC02Et/ CuO [Ns = A(/7-toluenesulfonyl-inimo)] and a conjugated ketone, for example, leads to the A-carboethoxy aziridine derivative.Calcium oxide has also been used to generate the nitrene.Other specialized reagents have also been used." ... 

Alkyl aryl ketones can be converted to arylacetic acid derivatives in an entirely different manner. The reaction consists of treatment of the substrate with silver nitrate and I2 or Br2, ° or with thallium nitrate, MeOH, and trimethyl orthoformate adsorbed on Montmorillonite K-10 clay, an acidic clay. ... 

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