Amine Organocatalysis of Remote, Chemoselective C(sp3)-H Hydroxylation was written by Hahn, Philip L.;Lowe, Jared M.;Xu, Yubo;Burns, Kevin L.;Hilinski, Michael K.. And the article was included in ACS Catalysis in 2022.Name: (1R,2S,5R)-2-Isopropyl-5-methylcyclohexanol This article mentions the following:
Authors introduce an organocatalytic approach for oxaziridinium-mediated C-H hydroxylation that employs secondary amines as catalysts. Authors also demonstrate the advantages of this operationally simple catalytic strategy for achieving high yielding and highly selective remote hydroxylation of compounds bearing oxidation-sensitive functional groups such as alcs., ethers, carbamates, and amides. By employing hexafluoroisopropanol as the solvent in the absence of water, a proposed hydrogen-bonding effect leads to, among other advantages, as high as ≥99:1 chemoselectivity for remote aliphatic hydroxylation of 2° alcs., an otherwise unsolved synthetic challenge normally complicated by substantial amounts of alc. oxidation Initial studies of the reaction mechanism indicate the formation of an oxaziridinium salt as the active oxidant and a C-H oxidation step that proceeds in a stereospecific manner via concerted insertion or hydrogen atom-transfer/radical rebound. Furthermore, preliminary results indicate that site selectivity can be affected by amine catalyst structure. In the experiment, the researchers used many compounds, for example, (1R,2S,5R)-2-Isopropyl-5-methylcyclohexanol (cas: 2216-51-5Name: (1R,2S,5R)-2-Isopropyl-5-methylcyclohexanol).
(1R,2S,5R)-2-Isopropyl-5-methylcyclohexanol (cas: 2216-51-5) belongs to alcohols. The oxygen atom of the strongly polarized O―H bond of an alcohol pulls electron density away from the hydrogen atom. This polarized hydrogen, which bears a partial positive charge, can form a hydrogen bond with a pair of nonbonding electrons on another oxygen atom. Tertiary alcohols cannot be oxidized at all without breaking carbon-carbon bonds, whereas primary alcohols can be oxidized to aldehydes or further oxidized to carboxylic acids.Name: (1R,2S,5R)-2-Isopropyl-5-methylcyclohexanol
Referemce:
Alcohol – Wikipedia,
Alcohols – Chemistry LibreTexts