Peroxyacids Alcohols

Chemical Properties. Alkyl peroxyesters are hydroly2ed more readily than the analogous nonperoxidic esters and yield the original acids and hydroperoxides from which they were prepared rather than alcohols and peroxyacids ... 

Pivalic acid [75-98-9] - [CARBOXYLICACIDS - TRIALKYLACETIC ACIDS] (Vol 5) - [AMYL ALCOHOLS] (Vol 2) - [AMYL ALCOHOLS] (Vol 2) - [CARBOXYLICACIDS-SURVEY] (Vol 5) -compared to peroxyacid [PEROXIDES AND PEROXIDE COMPOUNDS - ORGANIC PEROXIDES] (Vol 18)... 

You are already familiar with the simple formation of epoxides 26 by the action of peroxyacids such as mCPBA on alkenes 27. They can equally well be made by cyclisation of chloro-alcohols 25 as in the Comforth addition of a Grignard reagent to an a-chloroketone and cyclisation in base.3... 

The aminocyclitol d-48 was synthesized from l-218 (Scheme 28).103 Since direct peroxyacid oxidation of the exo-methylene group of compound l-218 had been shown to give selectively the undesired /<-spiro epoxide,35 102 it was first converted into l-219, followed by oxidation with m-CPBA to give the desired x-spiro epoxide d-220 (80%). The alcohol d-221 obtained in 73% yield by reductive cleavage of epoxide d-220 with lithium triethylborohydride (LiBHEt3) in THF was formed as a 2 3 mixture of two alcohols. However, hydrolysis of d-221 with hydrochloric acid gave d-48 (94%), which was further characterized by conversion into the pentaacetyl derivative 222 (82%). 

Epoxide 109 is opened with Me3SiBr (Ph3P-catalysed) and another elimination with DBU gives the allylic alcohol 117. The epoxidation that follows is controlled in a couple of ways. Firstly, the axial alcohol can direct the reagent (the same peroxyacid used to make 109) to the bottom face of the six-membered ring which is also the less hindered side of the molecule (opposite the lactone bridge) 118. The synthesis is completed with basic methanolysis of the lactone 118 to give racemic methyl shikimate 116. 

The action of peroxyacids, such as Caro s acid, on cyclic ketones affords co-hydroxy carboxylic acids or their lactones, the latter being convertible into co-hydroxy carboxylic esters by the action of an alcohol and an acid cyclohexanone, for instance, gives a 6-hydroxyhexanoic ester in this way 126,127... 

Primary alcohols are oxidized to carboxylic acids by chromium-containing reagents and to aldehydes by PCC or a Swem oxidation. Secondary alcohols are oxidized to ketones. Tollens reagent can oxidize only aldehydes. A peroxyacid oxidizes an aldehyde to a carboxylic acid, a ketone to an ester (in a Baeyer-Villiger oxidation), and an alkene to an epoxide. Alkenes are oxidized to 1,2-diols by potassium permanganate (KMn04) in a cold basic solution or by osmium tetroxide (OSO4). 

---