Ethyl phenylglyoxylate

An alternative photoinduced pathway has been identified in the photolysis of the meso-ionic oxathiazolone (335). Irradiation in ethanol in the presence of oxygen yields ethyl phenylglyoxylate (340 65%), ethyl benzoate (3%), and benzonitrile (21%). The postulated intermediates (Fig. 5) have been spectroscopically identified by photolysis in ether-isopentane-ethanol-glass at 85°K. ... 

The oxidation of ethyl pyruvate and ethyl phenylglyoxylate with per-oxyphthalic acid at 20-22 °C produces, after 48 and 90 h, mixed anhydrides of ethylcarbonic acid and acetic and benzoic acids, respectively [334]. 

Irradiation of ethyl phenylglyoxylate (114) leads to the formation of ethyl O-benzoylmandelate (115), ethyl O-acetylmandelate, and biphenyl triketone (116)... 

Novel chiral bis(1,4-dihydronicotinamide) derivatives bearing an 5-prolinamide moiety were prepared and used to reduce ethyl phenylglyoxylate and other substrates. High optical yields of the... 

Though the attempts to synthesize ethyl 2-hydroxy-2-phenyl-3-methylene-4 oxopentanoate via DABCO-catalyzed coupling of methyl vinyl ketone with ethyl phenylglyoxylate (a-keto ester) were unsuccessful, the chalcogeno-MBH reaction between a-keto esters and alkyl vinyl ketones proceeded smoothly under the catalytic influence of dimethyl sulfide in the presence of TiCU, affording 2-aryl-2-hydroxy-3-methylene-4-oxoalkanoates 297 in moderate to good yields (Scheme 2.163). ... 

Ketones have been also used as electrophiles for the synthesis of natural products. Thus, the partial synthesis of oxybutynin (ditropan) has been accomplished by the aldol reaction between cyclohexanone (3b) and ethyl phenylglyoxylate (23, R = Ph, R =EtO, Scheme 4.9) [69]. Also using a diastereoselective approach the synthesis of 3-functionalized 3-hydroxy-P-lactams has been achieved with good yields and total diastereoselectivity [70]. 

---