With pyridinium chlorochromate

Oxidation of tim5-4-(2,2,2-tnfluoro-l-hydroxy 1 tnfluoromethylethyl)cyclo-hexanol with pyridinium chlorochromate results m the correspondmg cyclic ketone whereas oxidation with nitnc acid m the presence of a catalyst causes ring cleavage [50] (equation 46)... 

What product would you obtain by reduction of digitoxigenin (Problem 27.39) with LiAl.H4 By oxidation with pyridinium chlorochromate ... 

The C2-symmetric epoxide 23 (Scheme 7) reacts smoothly with carbon nucleophiles. For example, treatment of 23 with lithium dimethylcuprate proceeds with inversion of configuration, resulting in the formation of alcohol 28. An important consequence of the C2 symmetry of 23 is that the attack of the organometallic reagent upon either one of the two epoxide carbons produces the same product. After simultaneous hydrogenolysis of the two benzyl ethers in 28, protection of the 1,2-diol as an acetonide ring can be easily achieved by the use of 2,2-dimethoxypropane and camphor-sulfonic acid (CSA). It is necessary to briefly expose the crude product from the latter reaction to methanol and CSA so that the mixed acyclic ketal can be cleaved (see 29—>30). Oxidation of alcohol 30 with pyridinium chlorochromate (PCC) provides alde-... 

Xb was utilized in the elaboration of the hydrindan XIII and subsequently compound XIV. We expected that Xa could be converted to XIII in the same manner as was in the Sih synthesis. This was confirmed in practice (Scheme II). Oxidation of 569 mg (2.68 mmol) of Xa with pyridinium chlorochromate in methylene chloride furnished 532 mg (94%) of enone Ila (7,21). Treatment of 130 mg of Xa witlj a slight excess of Jones reagent (3,22) afforded 126 mg (98%) of Ila. Allylic brominatlon of Ila with a 20% excess of N-bromosuccinimide (NBS) in refluxing carbon tetrachloride provided Xlla in 98% yield. 

A biomimetic synthesis of benzo[c]phenanthridine alkaloids from a protoberberine via the equivalent of a hypothetical aldehyde enamine intermediate has been developed (130,131). The enamide 230 derived from berberine (15) was subjected to hydroboration-oxidation to give alcohol 231, oxidation of which with pyridinium chlorochromate afforded directly oxyche-lerythrine (232) instead of the expected aldehyde enamide 233. However, the formation of oxychelerythrine can be rationalized in terms of the intermediacy of 233 as shown in Scheme 41. An alternative and more efficient... 

The pyranocoumarin 105 can be prepared via a three-component Diels-Alder reaction between 4-hydroxycoumarin, ethyl vinyl ether and an a-dicarbonyl compound. Similarly to the above, upon treatment of 105 with sulfuric acid in THF, hydrolysis and rearrangement occur to give the furofurochromenone 106. The hemiacetal functionality in 106 may then be oxidized with pyridinium chlorochromate (PCC) to give the lactone 107 <2001EJ03711> (Scheme 28). 

A. P. Rauter, F. Piedade, T. Almeida, R. Ramalho, M. J. Ferreira, R. Resende, J. Amado, H. Pereira, J. Justino, A. Neves, F. V. M. Silva, and T. Canda, Sugar bislactones by one-step oxidative dimerisation with pyridinium chlorochromate versus regioselective oxidation of vicinal diols, Carbohydr. Res., 339 (2004) 1889-1897. 

Oxidation of the hydroxyl group in 186 with pyridinium chlorochromate (PCC) in CH2CI2 affords the aldehyde 197. The reduction of 197 back to 186 is possible in EtOH in the presence of TiCl4, whereas upon treatment of 197 with diisobutyl-aluminium hydride a competitive reaction with the fullerene core was observed. 

Oxidation of 2,5-dialkylfurans with pyridinium chlorochromate results in high yields of a,(3-unsaturated y-dicarbonyl compounds (Scheme 25) (82S245, 80T661). Similar results are obtained by peracid oxidation of furans (see review (90MI206-01)). The acid most frequently used is MCPBA. It is assumed that the first step involves epoxidation as shown in Scheme 25 (83CL1771). 

Oxidation of 8-hydroxymethyl-2-isopropyl-l 1 //-pyrido[2,l-b]quinazolin-11-one with pyridinium chlorochromate in methylene chloride gave the 8-carboxaldehyde, which was converted into its 8-aminomethyl derivatives by reacting with amines followed by reduction of the Schiff bases with sodium cyanoborohydride in acetic acid (87JOC2469). 

General Procedure for Oxidation of Alcohols to Aldehydes and Ketones with Pyridinium Chlorochromate (PCC)237... 

A novel one-pot tandem oxidation-cyclization-oxidation process was successfully applied in the transformation of unsaturated alcohols 250 [Eq. (5.315)].860 The intermediate aldehyde formed by oxidation with pyridinium chlorochromate (PCC) undergoes a carbonyl-ene cyclization followed by an additional oxidation to form 3-substituted piperidinones. 

Oxidation of glycol esters to ene-S-lactones. Reaction of glycal esters with m-chloroperbenzoic acid involves the expected epoxidation followed by cleavage of the oxide by the /n-chlorobenzoic acid formed. However, in the presence of BF3, the reaction produces a,/ -unsaturated 5-lactones, usually in excellent yield. This oxidation is also possible with pyridinium chlorochromate and BF3 as catalyst, but in lower yield.1... 

Although in principle naturally occurring (—)-galanthamine could have been prepared by an identical sequence of reactions commencing with D-tyrosine, an alternate route to 319, the enantiomer of 314, was developed. Thus, epimeriza-tion of the methyl ester group at C-6 of the A -trifluoroacetamide derived from 315 followed by oxidation of the allylic alcohol with pyridinium chlorochromate furnished 319 in 78% optical purity, albeit in low chemical yield. Since 319 could be converted to (-)-galanthamine (291) by the same sequence of reactions outlined for the transformation of 314 to (+)-galanthamine, its preparation may be considered to represent a formal total synthesis of 291 from L-tyrosine (163). 

The secondary alcohol is readily oxidized with pyridinium chlorochromate (PCC)25 (65) which is commercially available or easily prepared by addition of pyridine to a solution of chromium(VI)-oxide in hydrochloric acid. 

---