Transition‐Metal‐Free Aerobic Oxidative Cleavage of CC Bonds in α‐Hydroxy Ketones and Mechanistic Insight to the Reaction Pathway

Abstract

Klarer Schnitt: Für die Titelreaktion wurde O2, das ideale Oxidans, als einziges Oxitationsmittel verwendet. Das Dimerintermediat (siehe Schema) und Isotopenmarkierungsexperimente mit 18O2 konnten teilweise den Reaktionsmechanismus aufklären.

Copper‐Catalyzed Aerobic Oxidative CC Bond Cleavage for CN Bond Formation: From Ketones to Amides

“…Recently, a few elegant examples of aerobic oxidative CC bond cleavage involving carbonyl compounds have been reported. Jiang and co‐workers7 reported a transition‐metal‐free aerobic oxidative CC bond cleavage of α‐hydroxyketones and subsequent esterification (Scheme ). The group of Bi and Liu8 reported a copper‐catalyzed C(CO)C(methyl) bond cleavage reaction under oxygen atmosphere, which terminates at the aldehyde stage without overoxidization (Scheme ).…”

Chemoselective Oxidative C(CO)C(methyl) Bond Cleavage of Methyl Ketones to Aldehydes Catalyzed by CuI with Molecular Oxygen

“…The chemoselective C(CO)C(α) bond cleavage of ketones is a fundamental reaction that has been extensively studied, and has been used for transformations into acids,6 esters,7 amides,8 ketones,9 and acyl‐metal complexes10 (Figure 1). Very recently, Jiang and co‐workers described an interesting oxidative cleavage and esterification of the CC bonds of α‐hydroxy ketones under metal‐free conditions 11. Berreau and co‐workers reported the regioselective CC bond cleavage of acireductones to acids by a model system of iron‐containing acireductone dioxygenase 12.…”

Chemoselective Oxidative C(CO)C(methyl) Bond Cleavage of Methyl Ketones to Aldehydes Catalyzed by CuI with Molecular Oxygen

“…Very recently, Jiang and co-workers described an interesting oxidative cleavage and esterification of the C À C bonds of a-hydroxy ketones under metal-free conditions. [11] Berreau and co-workers reported the regioselective C À C bond cleavage of acireductones to acids by a model system of iron-containing acireductone dioxygenase. [12] However, to the best of our knowledge, an oxidative C(CO)ÀC(a) bond cleavage of ketones that completely terminates at the aldehyde stage has not been described, this is probably due to easy overoxidation to the carboxylic acids.…”