Epoxides oxidative cleavage

Silica gel-based catalytic systems have been described as efficient promoters for a number of organic reactions.28 Illustrative examples include the oxidative cleavage of double bonds catalyzed by silica-supported KM11O4,29 reaction of epoxides with lithium halides to give /i-halohydrins performed on silica gel,30 selective deprotection of terf-butyldimethylsilyl ethers catalyzed by silica gel-supported phosphomolybdic acid (PMA),31 and synthesis of cyclic carbonates from epoxides and carbon dioxide over silica-supported quaternary ammonium salts.32... 

Cyelobutanone has been prepared by (1) reaction of diazomethane with ketene,4 (2) treatment of methylenecyclobutane with performic acid, followed by cleavage of the resulting glycol with lead tetraacetate,s (3) ozonolysis of methylenecyclobutane, (4) epoxidation of methylene-cyclopropane followed by acid-catalyzed ring expansion,7 and (5) oxidative cleavage of cyclobutane trimethylene thioketal, which in turn is prepared from 2-(co-chloropropyl)-l,3-dithiane.8... 

The formation of unsaturated cyanohydrins (from a, -unsaturated aldehydes) is of further advantage as these products possess an additional synthetic potential. As in the saturated cyanohydrins (above in Scheme 6) they possess the same opportunities for elaboration of the hydroxyl or nitrile moiety, although the presence of the carbon-carbon double bond offers the possibility for additional transformations to be performed such as additions [108], oxidative cleavage [117,118] and epoxidation [119] (Scheme 7). Thus, these highly functionalised chiral units can be of greater importance to an organic chemist. 

A fully stereocontrolled preparation of 499 has recently been completed by Paquette and coworkers When triene 508 was treated with /7-toluenesulfonyl-acetylene, highly stereoselective addition from the endo surface occurred to deliver an adduct which was directly epoxidized (Scheme XLI). The proximity of the two jc bonds in 509 allows for ready photocyclization. Oxidative cleavage of 510 afforded... 

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