Buchner-Curtius-Schlotterbeck reaction

Carbonyl compounds react with aliphatic diazo compounds to deliver homologated ketones. 

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The reaction, as originally carried out, is of little contemporary use. Metal-mediated catalysis is more-often applied, where the reactive species are metal carbenoids. Buchner-Curtius-Schlotterbeck Reaction... 

This reaction was first reported by Buchner and Curtius in 1885 and subsequently by Schlotterbeck in 1907. It is the reaction for forming ketones from aldehydes and aliphatic diazo compounds and is thus known as the Buchner-Curtius-Schlotterbeck reaction. This reaction has been extended to synthesize jS-keto esters from the condensation between diazo esters and aldehydes." It should be pointed out that epoxides and aldehydes are also produced in this reaction, and the preparation of keto esters can also be performed in the presence of Lewis acids or via a two-step process involving an Aldol Reaction of diazo ester and aldehyde followed by the oxidative elimination of nitrogen. ... 

Schlotterbeck (see Buchner-Curtius-Schlotterbeck Reaction) Schmidt (see Bohn-Schmidt Reaction)... 

Buchner-Curtius-Schlotterbeck reaction 7, 816 10, 606 —, improved, stepwise 19, 861 Buffer solns. s. Acetate buffer, Citric acid —, Citric acid-phosphate —, Phosphate — Bunte salts s. Thiosulfuric acid S-monoesters Butadiene dioxide... 

Since Theodor Curtius reported the synthesis of ethyl diazoacetate in 1883, Buchner had investigated its reactions with carbonyl compounds, alkenes, alkynes, and aromatic compounds for more than 30 years.His extensive contributions in this area resulted in two reactions named in his honor the Buchner-Curtius-Schlotterbeck reaction (formation of ketones from aldehydes and aliphatic diazo compounds) and the Buchner reaction. The prototypical example of the latter involves the thermal or photochemical reaction of ethyl diazoacetate with benzene to give (via norcaradiene 7) a mixture of four isomeric cycloheptatrienes 8-11. Initially, Buchner believed that a single norcaradiene product 7 was generated from this reaction, but later, he realized that the hydrolysis of the product afforded a mixture of four isomeric carboxylix acids. The norcaradiene formulation persisted until 1956 when Doering reinvestigated this reaction. ... 

The reaction of diazoalkanes with carbonyl-containing compounds dates back to observations made by Buchner and Curtius as early as 1885 [56]. Although others examined this novel reactivity pattern [57,58], Schlotterbeck is largely credited with uncovering the merger of aldehydes and diazoalkanes in 1907 [59, 60]. Schlotterbeck was able to confirm by careful experimentation that various aliphatic aldehydes afforded the corresponding methyl ketones when treated with diazomethane. The reaction of aldehydes with diazomethane to form methyl ketones (Scheme 3) later became known as the Buchner-Curtius—Schlotterbeck reaction [61]. Application of this chain elongation to ketmies and eventually cycloalkanones did not come until several decades later and required a critical new discovery. 

Scheme 3 The Buchner-Curtius-Schlotterbeck reaction (methyl ketone synthesis)...

Stepwise improved Buchner-Curtius-Schlotterbeck reaction... 

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