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In organic chemistry, a hemiacetal is a functional group the general formula R 1 R 2 C(OH)OR, where R 1, R 2 is a hydrogen atom or an organic substituent. They generally result from the nucleophilic addition of an alcohol (a compound with at least one hydroxy group ) to an aldehyde ( R−CH=O ) or a ketone ( R 2 C=O ) under acidic conditions.
This forms an intramolecular hemiacetal. If reaction is between the C-4 hydroxyl and the aldehyde, a furanose is formed instead. [1] The pyranose form is thermodynamically more stable than the furanose form, which can be seen by the distribution of these two cyclic forms in solution. [2]
In contrast to variations of R, both R' groups are organic fragments. If one R' is a hydrogen, the functional group is instead a hemiacetal, while if both are H, the functional group is a ketone hydrate or aldehyde hydrate. Formation of an acetal occurs when the hydroxyl group of a hemiacetal becomes protonated and is lost as water.
The whole mechanism of acetal formation from hemiacetal is drawn below. Acid catalyzed acetal formation from the corresponding hemiacetal Acetals, as already pointed out, are stable tetrahedral intermediates so they can be used as protective groups in organic synthesis.
Cis-3-hexenal is generated by conversion of linolenic acid to the hydroperoxide by the action of a lipoxygenase followed by the lyase-induced formation of the hemiacetal. [ 5 ] It must be noted, however, that this enzyme catalyzed path follows a different mechanism from the usual Schenck ene reaction.
Hemiaminal formation is a key step in an asymmetric total synthesis of saxitoxin: [10] In this reaction step the alkene group is first oxidized to an intermediate acyloin by action of osmium(III) chloride, oxone (sacrificial catalyst) and sodium carbonate (base).
D-ribose in itself is a hemiacetal and in equilibrium with the pyranose 3. In aqueous solution ribose is 75% pyranose and 25% furanose and a different acetal 4 is formed. Selective acetalization of carbohydrate and formation of acetals possessing atypical properties is achieved by using arylsulfonyl acetals.
The chemical structure of ribose in its furanose form. The wavy bond indicates a mixture of β-ribofuranose and α-ribofuranose. The furanose ring is a cyclic hemiacetal of an aldopentose or a cyclic hemiketal of a ketohexose.