Aldehydes oxidative cleavage

In nature, vitamin A aldehyde is produced by the oxidative cleavage of P-carotene by 15,15 - P-carotene dioxygenase. Alternatively, retinal is produced by oxidative cleavage of P-carotene to P-apo-S -carotenal followed by cleavage at the 15,15 -double bond to vitamin A aldehyde (47). Carotenoid biosynthesis and fermentation have been extensively studied both ia academic as well as ia iadustrial laboratories. On the commercial side, the focus of these iavestigations has been to iacrease fermentation titers by both classical and recombinant means. 

Concern for the conservation of energy and materials maintains high interest in catalytic and electrochemistry. Oxygen in the presence of metal catalysts is used in CUPROUS ION-CATALYZED OXIDATIVE CLEAVAGE OF AROMATIC o-DIAMINES BY OXYGEN (E,Z)-2,4-HEXADIENEDINITRILE and OXIDATION WITH BIS(SALI-CYLIDENE)ETHYLENEDIIMINOCOBALT(II) (SALCOMINE) 2,6-DI-important industrial method, is accomplished in a convenient lab-scale process in ALDEHYDES FROM OLEFINS CYCLOHEXANE-CARBOXALDEHYDE. An effective and useful electrochemical synthesis is illustrated in the procedure 3,3,6,6-TETRAMETHOXY-1,4-CYCLOHEX ADIENE. ... 

We ve already discussed two methods of aldehyde synthesis oxidation of primary alcohols and oxidative cleavage of alkenes. 

Alkenes with at least one vinjdic hydrogen undergo oxidative cleavage when treated with ozone, yielding aldehydes (Section 7.9). If the ozonolysis reaction is carried out on a cyclic alkene, a dicarbonyl compound results. 

Methods of synthesis for carboxylic acids include (1) oxidation of alkyl-benzenes, (2) oxidative cleavage of alkenes, (3) oxidation of primary alcohols or aldehydes, (4) hydrolysis of nitriles, and (5) reaction of Grignard reagents with CO2 (carboxylation). General reactions of carboxylic acids include (1) loss of the acidic proton, (2) nucleophilic acyl substitution at the carbonyl group, (3) substitution on the a carbon, and (4) reduction. 

Terminal alkynes can be converted by a process of hydrosilylation followed by oxidative cleavage into carboxylic acids (10). An alternative basic" cleavage yields the corresponding aldehydes. 

For a review of metal ion-catalyzed oxidative cleavage of alcohols, see Trahanovsky, W.S. Methods Free-Radical Chem. 1973, 4, 133. For a review of the oxidation of aldehydes and ketones, see Verter, H.S. in Zabicky The Chemistry of the Carbonyl Group, pt. 2 Wiley NY, 1970, p. 71. 

The obvious Vfittig disconnection gives stabilised ylid (5fi) and keto-aldehyde (57). We have used many such long-chain dicarbonyl compounds in this Chapter and they are mostly produced from available alkenes by oxidative cleavage (e.g. ozonolysis). In this case, cyclic alkene (58) is the right starting material, and this can be made from alcohol (59) by elimination,... 

Osmium tetroxide used in combination with sodium periodate can also effect alkene cleavage.191 Successful oxidative cleavage of double bonds using ruthenium tetroxide and sodium periodate has also been reported.192 In these procedures the osmium or ruthenium can be used in substoichiometric amounts because the periodate reoxidizes the metal to the tetroxide state. Entries 1 to 4 in Scheme 12.18 are examples of these procedures. Entries 5 and 6 show reactions carried out in the course of multistep syntheses. The reaction in Entry 5 followed a 5-exo radical cyclization and served to excise an extraneous carbon. The reaction in Entry 6 followed introduction of the allyl group by enolate alkylation. The aldehyde group in the product was used to introduce an amino group by reductive alkylation (see Section 5.3.1.2). 

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