Home > Community > What is the mechanism for the oxidation of a lactol to a lactone?
Upvote

21

Downvote
+ Alcohols
+ Chemistry
Posted by
Kai Rabenstein

What is the mechanism for the oxidation of a lactol to a lactone?

Bill Jones  Follow

Lactols are basically aldehydes in ring formation.

What happens is the lactols unwind in solution into chain formation and it is here that they are oxidized to carboxylic acid by something like Tollen's reagent. Then when they reform, they do so in lactone form.

More

Upvote

VOTE

Downvote
Dr Balfaa  Follow
The lactol does not have to open to the hydroxy aldehyde to oxidize. The aldehyde hydrates before oxidation. The lactol is in effect a hydrated aldehyde. PCC oxidations of primary alcohols often give esters as by-products. PCC and Collins oxidation of 1,4-butanediol afford butyrolactone and not succindialdeyde.More
Upvote

VOTE

Downvote
Dick Hughes  Follow

Methyl(trifluoromethyl)dioxirane (TFDO) in 1,1,1‐trifluoro‐2‐propanone (TFP)may be able to do your sought oxidation (see image [1] below): In there, cyclic ethers (shown example is tetrahydropyran) yield lactones by subsequent oxidation of a stable cyclic hemiacetal intermediate such as lactol in your case.

1

It is considered as selective and reactive oxidizing agent, capable of epoxidation of unreactive alkenes and arenes, oxyfunctionalization of alkanes, and oxidation of alcohols and ethers in following reference: Encyclopedia of Reagents for Organic Synthesis (1; March 2016); 11 pages. (https://doi.org/10.1002/047084289X.rm267.pub3)

You may also read: Oxidations by methyl(trifluoromethyl)dioxirane. 5. Conversion of alcohols into carbonyl compounds: J. Am. Chem. Soc., 1991, 113(6), 2205–2208 (DOI: 10.1021/ja00006a044).

More

Upvote

VOTE

Downvote