2021
DOI: 10.3762/bjoc.17.172
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α-Ketol and α-iminol rearrangements in synthetic organic and biosynthetic reactions

Abstract: In the presence of a suitable acid or base, α-hydroxyaldehydes, ketones, and imines can undergo isomerization that features the 1,2-shift of an alkyl or aryl group. In the process, the hydroxy group is converted to a carbonyl and the aldehyde/ketone or imine is converted to an alcohol or amine. Such α-ketol/α-iminol rearrangements are used in a wide variety of synthetic applications including asymmetric synthesis, tandem reactions, and the total synthesis and biosynthesis of natural products. This review explo… Show more

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Cited by 6 publications
(2 citation statements)
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“…To elucidate the process of this base-controlled selective controllable skeletal rearrangement transformation of hexahydro-4 H -indol-4-ones, a possible mechanism has been proposed based on some previous literature. , As shown in Scheme , the deprotonation of 1a initiated in the presence of LiOH to give A , and then, the lithium ion was complexed with the two carbonyl groups in the structure to form the intermediate B , which underwent an α-ketol rearrangement to give the desired product 2a (path a). The initiation process for the formation of 8-alkenyl oxepane-2,6-dione 3a is shown in path b.…”
mentioning
confidence: 99%
“…To elucidate the process of this base-controlled selective controllable skeletal rearrangement transformation of hexahydro-4 H -indol-4-ones, a possible mechanism has been proposed based on some previous literature. , As shown in Scheme , the deprotonation of 1a initiated in the presence of LiOH to give A , and then, the lithium ion was complexed with the two carbonyl groups in the structure to form the intermediate B , which underwent an α-ketol rearrangement to give the desired product 2a (path a). The initiation process for the formation of 8-alkenyl oxepane-2,6-dione 3a is shown in path b.…”
mentioning
confidence: 99%
“…Taking inspiration from the Amadori and α-iminol rearrangements (35,36), we believed that appropriate β-oxidation of the enamine to the hydroxy-iminium ion should then follow a related mechanistic course and tautomerize to the thermodynamically more stable α-aminoketone. Indeed, enamine oxidation has been demonstrated on "N-deactivated" substrate classes, e.g.…”
mentioning
confidence: 99%