63703-34-4Relevant academic research and scientific papers
Morpholinosulfur trifluoride (morph-DAST)-mediated rearrangement in the fluorination of cyclic α,α-dialkoxy ketones toward 1,2-dialkoxy-1,2-difluorinated compounds
Surmont, Riccardo,Verniest, Guido,De Groot, Alex,Thuring, Jan Willem,De Kimpe, Norbert
scheme or table, p. 2751 - 2756 (2010/12/25)
The deoxofluorination of cyclic α,α-dialkoxy ketones with morpholinosulfur trifluoride (Morph-DAST) resulted in 1,2-dialkoxy-1,2- difluorinated carbo- and heterocyclic compounds. The reaction proceeds via a 1,2-alkoxy migration leading to mixtures of cis-
Highly stereoselective synthesis of new α-amino-β-hydroxy six-membered heterocyclic phosphonic acids, serine analogues
Louaisil, Nicolas,Rabasso, Nicolas,Fadel, Antoine
scheme or table, p. 8587 - 8595 (2009/12/09)
The synthesis of 2-hydroxy-4-heterocyclic phosphonic acids was achieved in a six-step sequence from the appropriate ketones. Thus, 2-hydroxyheterocyclic ketone acetals were prepared and then esterified by N-Boc-l-phenylalanine, used as a chiral auxiliary. The resulting heterocyclic acetal esters gave by a one-pot reaction bicyclic ketimines. These imines underwent nucleophilic addition with phosphite to provide efficiently and stereoselectively, under kinetic control, bicyclic aminophosphonates. Cleavage of the phenylalanine moiety by oxidation followed by acidic hydrolysis of the resulting heterocyclohexylphosphonates provided the new (4-amino-3-hydroxypiperidin-4-yl)-, (4-amino-3-hydroxytetrahydro-2H-pyran-4-yl)- and (1-amino-2-hydroxycyclohexyl)phosphonic acids.
α-Hydroxylation of carbonyls using iodine
Zacuto, Michael J.,Cai, Dongwei
, p. 447 - 450 (2007/10/03)
The α-hydroxylation of ketones and aldehydes to α-hydroxyketals mediated by iodine under basic conditions in MeOH is described. Enolates generated under the reaction conditions are iodinated and the resulting α-iodocarbonyl is transformed into the hydroxyketal. The use of iodine for this chemistry represents an economical and practical alternative to existing methods for this transformation.
The reaction of enaminones with grignard reagents: Synthesis of α,β- unsaturated ketones
Fontenas,Ait-Haddou,Bejan,Balavoine
, p. 1743 - 1753 (2007/10/03)
Enaminones in toluene react with Grignard reagents in tetrahydrofuran at 0-25 °C, to give selectively and with high yields the corresponding α,β- unsaturated ketones.
Indirect electrochemical oxidation of cyclic ketones: Influence of ring size, mediator and supporting electrolyte on the result of the reaction
Barba, Fructuoso,Elinson, Michail N.,Escudero, Jose,Feducovich, Sergey K.
, p. 4427 - 4436 (2007/10/03)
The result of the indirect electrochemical oxidation of cyclic ketones in methanol in an undivided cell in the presence of sodium halides depends on the ring size of ketone and the type of mediator. Selectivity of the reaction in some cases and current efficiency are increased by addition of supporting electrolyte - sodium hydroxide. Formation of cyclic 2,2-dimethoxycycloalkanols and the electrochemically induced Favorskii rearrangement with the formation of methyl cycloalkencarboxylates containing in the ring one carbon atom less than starting ketone are the main ways of the indirect electrochemical oxidation of cyclic ketones.
Indirect electrochemical oxidation of cyclic ketones: Strong influence of ring size on the result of the reaction
Barba, Fructuoso,Elinson, Michail N.,Escudero, Jose,Feducovich, Sergey K.
, p. 5759 - 5762 (2007/10/03)
The result of the indirect electrochemical oxidation of cyclic ketones in methanol in the undivided cell in the presence of sodium iodide depends on the ring size. Cyclopentanone affords 2,2-dimethoxycyclopentanone. While cyclohexanone gives rise 2,2-dimethoxycyclo-hexanol, and cyclic ketones with higher ring size undergo new type of the electrochemically induced Favorskii rearrangement with the formation of methyl cycloalkencarboxylates containing in the ring on the one carbon atom less than starting ketone. So the simple electrocatalytic system can distinguish the ring size of cyclic ketones.
Ring-Chain Tautomerism Provides a Route to 7a-Hydroxy-3a-methyl-2,7-dioxoperhydrobenzofuran. Synthesis of the Hydroxy γ-Lactone Substructure of Myrocin and Other Bioactive Natural Products
Langschwager, Wolf,Hoffmann, H. Martin R.
, p. 797 - 802 (2007/10/02)
(2-Oxocyclohexyl)acetic acid 10 was converted into bicyclic alkoxy γ-lactones 12a-d via intermediate chloro lactone 11 and alkanolysis.Similarly, lactones 15a,b and 18 were prepared.In contrast, simple ring-chain tautomerism directly afforded the title heterocycle 28, a crystalline, stable and welldefined compound.The angular methyl group seems essential for the spontaneous lactonization. 5,5-Dialkoxy-4-oxocarboxylic acids 26a, b without an angular methyl group did not cyclize to bicyclic hydroxy γ-lactones. - Key Words: Hydroxy lactone, 5-membered, (lactol) tautomer / 4-Oxocarboxylic acids / Keto-cyclol tautomerism.
Electrochemical oxidation of ketones in methanol in the presence of alkali metal bromides
Nikishin, Gennady I.,Elinson, Michail N.,Makhova, Irina V.
, p. 895 - 905 (2007/10/02)
Electrochemical oxidation of methyl ketones in methanoi in the presence of alkali metal bromides affords methyl carboxylates. Benzyl alkyl ketones are transformed under similar conditions into methyl 3-phenylalkanoates, while ketones lacking σ-benzyl or σ-methyl group are oxidized into σ-hydroxyketals.
The Reactions of α-Arylsulfonoxy Ketones with Nucleophiles
Hoffman, Robert V.,Jankowski, Bryan C.,Carr, C. Sean,Duesler, Eileen N.
, p. 130 - 135 (2007/10/02)
α-(p-Nitrophenyl)sulfonoxy ketones can be converted to α-hydroxy ketals and α-hydroxy ketones by reaction with potassium carbonate and basic or acidic workup, respectively.They also react with amines to give α-amino ketones in high yields.Nonnucleophilic amines give an intramolecular aromatic substitution in the derived enolate.Factors which dictate the reaction patterns in these compounds are discussed.
