Mesityl Oxide and Diacetone Alcohol in the Bucherer Synthesis of Hydantoins

Henze, Henry R.; Thompson, Thomas R.; Speer, R. J.

doi:10.1021/jo01189a005

Cited by 3 publications

(2 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Because of aqueous reaction conditions, there is no need for dry solvents. Most commonly, a mixture of water with ethanol (or methanol) or methanol itself is employed [ 138 , 139 , 140 , 141 , 142 , 143 , 144 , 145 , 146 , 147 , 148 , 149 , 150 , 151 , 152 , 153 , 154 , 155 , 156 , 157 , 158 , 159 , 160 , 161 , 162 , 163 , 164 , 165 , 166 , 167 , 168 , 169 , 170 , 171 , 172 , 173 , 174 , 175 , 176 , 177 , 178 , 179 , 180 , 181 , 182 , 183 , 184 , 185 , 186 , 187 , 188 ...…”

Section: Experimental Conditionsmentioning

confidence: 99%

The Bucherer–Bergs Multicomponent Synthesis of Hydantoins—Excellence in Simplicity

et al. 2021

View full text Add to dashboard Cite

Hydantoins and their hybrids with other molecules represent a very important group of heterocycles because they exhibit diverse biological and pharmacological activities in medicinal and agrochemical applications. They also serve as key precursors in the chemical or enzymatic synthesis of significant nonnatural α-amino acids and their conjugates with medical potential. This review provides a comprehensive treatment of the synthesis of hydantoins via the Bucherer–Bergs reaction including the Hoyer modification but limited to free carbonyl compounds or carbonyl compounds protected as acetals (ketals) and cyanohydrins used as starting reaction components. In this respect, the Bucherer–Bergs reaction provides an efficient and simple method in the synthesis of important natural products as well as for the preparation of new organic compounds applicable as potential therapeutics. The scope and limitations, as well as a comparison with some other methods for preparing hydantoins, are also discussed.

show abstract

Section: Experimental Conditionsmentioning

confidence: 99%

The Bucherer–Bergs Multicomponent Synthesis of Hydantoins—Excellence in Simplicity

et al. 2021

View full text Add to dashboard Cite

show abstract

“…both 2-(2-hydroxyisobutyl) -2-methyl-3,4,5-triketopyrrole (LXXIV) and 5-methyl-5-(2methy 1-1 -propenyl) -hydantoin (LXXV) may be obtained by the reaction of mesityl oxide with potassium cyanide and ammonium carbonate(68). The formation of both of these materials illustrates Type 1 condensation except that LXXIV also contains a hydroxylic function arising from the addition of the elements of water to the carbon-carbon double bond.…”

mentioning

confidence: 99%

The Reactions of Mesityl Oxide.

Hauser¹

1963

Chem. Rev.

View full text Add to dashboard Cite

Hydrocyanation of Conjugated Carbonyl Compounds

Nagata

Yoshioka

1977

Organic Reactions

View full text Add to dashboard Cite

Hydrogen cyanide adds to a multiple bond in the presence of an appropriate catalyst. The process is called hydrocyanation. The addition to an α,β‐unsaturated carbonyl compound gives a 1,2 adduct, α‐cyanohydrin, and a 1,4 adduct, β‐cyano ketone. Both 1,2 and 1,4 additions are reversible in principle, but in the presence of a base the reverse 1,2 addition is much faster than the reverse 1,4 reaction, leading to the 1,4 adduct as a major (usually sole) product. In this sense conjugate hydrocyanation is a special case of the Michael reaction. Predominance of 1,2 or 1,4 addition depends on the substrate structure, the reagent, and the reaction conditions. In this chapter 1,2 addition is discussed only when necessary. This chapter deals chiefly with the 1,4 addition and, more generally, with conjugate addition including that on conjugated polyethylenic compounds giving 1,6 or more extended conjugated adducts. Carbonyl substrates include ketones, aldehydes, carboxylic acid derivatives, carbonitriles, and carboimines. Also included are β‐functionalized carbonyl compounds, and π‐allylpalladium complexes, that generate α,β‐unsaturated carbonyl compounds, under hydrocyanation conditions. Although hydrogen cyanide adds to α,β‐unsaturated compounds activated by other groups such as nitro and sulfone, these reactions are not considered in this chapter. The first example of 1,4 addition of hydrogen cyanide to α,β‐unsaturated carbonyl derivatives appeared more than a century ago, in 1873, when Claus prepared tricarballylic acid (1,2,3‐propanetricarboxylic acid) by heating an ethanolic solution of 2,3‐dichloropropene and potassium cyanide in a sealed tube. The discovery in 1903 that the reactive species in hydrocyanation is the cyanide anion, CN − , and that the rate of the reaction is proportional to the concentration of CN −8 , formed the foundation for active study of hydrocyanation chemistry. A fundamental procedure for conjugate hydrocyanation was developed which used 2 molar equivalents of potassium cyanide and 1 molar equivalent of acetic acid in aqueous alcohol. The reaction mode was clarified by Ingold and Michael in the 1930s. Many chemists began extensive application of the reaction to organic syntheses, and attempts were made to explore improved procedures with higher efficiency and fewer side reactions. Detailed reviews cover developments of conjugate hydrocyanations up to the 1950s. In recent years conjugate hydrocyanation has been used in total syntheses of complex natural products such as terpenes, steroids, and alkaloids. However, conventional procedures using hydrogen cyanide in the presence of a base or an alkali or alkaline‐earth metal cyanide were not efficient. Furthermore, the efficiency could not be improved without increasing side reactions. The difficulty was overcome in 1962 when methods using organoaluminum compounds were discovered by Nagata and co‐workers. They developed two new hydrocyanation methods, one involving a combination of hydrogen cyanide and an alkylaluminum and the other an alkylaluminum cyanide, both in an aprotic solvent. Applications of the new methods have led to total syntheses of complex natural products having a methyl, a functionalized methyl, or a carbon bridge at an angular position.

show abstract

Mesityl Oxide and Diacetone Alcohol in the Bucherer Synthesis of Hydantoins

Cited by 3 publications

References 8 publications

The Bucherer–Bergs Multicomponent Synthesis of Hydantoins—Excellence in Simplicity

The Bucherer–Bergs Multicomponent Synthesis of Hydantoins—Excellence in Simplicity

The Reactions of Mesityl Oxide.

Hydrocyanation of Conjugated Carbonyl Compounds

Contact Info

Product

Resources

About