18956-05-3Relevant academic research and scientific papers
Diastereoselective Hydroxylation of Titanium Enolates with tert-Butylhydroperoxide
Schulz M.,Kluge, R.,Schuessler, M.,Hoffmann, G.
, p. 3175 - 3180 (1995)
The oxidation of titanium enolates with tert-butylhydroperoxide has been investigated and the main reaction products, the corresponding α-hydroxyketones 7a-f, isolated.The highest diastereoselectivities (>95percent de) were obtained, when titanium enolates of camphor 2d-6d were employed.For comparison, the oxidation of the enolates with dimethyldioxirane is discussed.
Ketone Enolates as Nucleophiles in Palladium-catalysed Allylic Alkylation
Fiaud, Jean-Claude,Malleron, Jean-Luc
, p. 1159 - 1160 (1981)
Lithium enolates from pentan-3-one, cyclohexanone, acetophenone, and mesityl oxide react with some representative (acyclic and cyclic) allylic acetates in a palladium-catalysed alkylation in good yields and under mild conditions; the substitution is shown
Palladium-catalyzed allylic alkylation of simple ketones with allylic alcohols and its mechanistic study
Huo, Xiaohong,Yang, Guoqiang,Liu, Delong,Liu, Yangang,Gridnev, Ilya D.,Zhang, Wanbin
supporting information, p. 6776 - 6780 (2014/07/08)
Allylic alcohols were directly used in Pd-catalyzed allylic alkylations of simple ketones under mild reaction conditions. The reaction proceeded smoothly at 20°C by the concerted action of a Pd catalyst, a pyrrolidine co-catalyst, and a hydrogen-bonding solvent, and does not require any additional reagents. A computational study suggested that methanol plays a crucial role in the formation of the π-allylpalladium complex by lowering the activation barrier. Concerted action: Allylic alcohols were directly used in the title reaction under mild conditions. The reaction smoothly proceeds by the concerted action of a Pd catalyst, a pyrrolidine co-catalyst, and a hydrogen-bonding solvent, and does not require any additional reagents. A computational study suggested that methanol plays a crucial role in the formation of the π-allylpalladium complex by lowering the activation barrier.
C-N bond cleavage of allylic amines via hydrogen bond activation with alcohol solvents in Pd-catalyzed allylic alkylation of carbonyl compounds
Zhao, Xiaohu,Liu, Delong,Guo, Hui,Liu, Yangang,Zhang, Wanbin
, p. 19354 - 19357 (2012/01/06)
Hydrogen-bond-activated C-N bond cleavage of allylic amines was realized in Pd-catalyzed allylic alkylation to form the C-C bond product. The method could be expanded to a series of allylic amines and carbonyl compounds with excellent results. It provides a new and convenient access to C-C bond formation based on Pd-catalyzed allylic alkylation of allylic amines by using only inexpensive alcohol solvents.
Palladium-Catalyzed Decarboxylative Allylic Alkylation of Allylic Acetates with β-Keto Acids
Tsuda, Tetsuo,Okada, Masahiro,Nishi, Sei-ichi,Saegusa, Takeo
, p. 421 - 426 (2007/10/02)
In the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium, β-keto acids react with allylic acetates at ambient temperature to produce α-allylic ketones in good yields with quantitative decarboxylation.This palladium-catalyzed decarboxylative allylic alkylation of allylic acetates with β-keto acids is characterized by high regio- and stereoselectivity.Allylation of β-keto acid takes place at the carbon atom bearing a carboxyl group.Allylic alkylation of allylic acetate with β-keto acid occurs at the less substituted end of the allyl group.The resultant carbon-carbon double bond of the α-allylic ketone has the E configuration.Allylic alkylation of lactone 25 with benzoylacetic acid proceeds preferably with retention of configuration, indicative of trans attack of the enolate on the (?-allyl)palladium intermediate from the opposite side of palladium even in the coexistence of free carboxylic acids.
Regioselective Lewis Acid-mediated α-sec-Alkylation of Carbonyl Compounds
Reetz, Manfred T.,Walz, Peter,Huebner, Friedhelm,Huettenhain, Stefan H.,Heimbach, Horst,Schwellnus, Konrad
, p. 322 - 335 (2007/10/02)
Carbonyl compounds such as ketones, aldehydes, acyloins, or carboxylic esters can be alkylated at the α-position via the corresponding O-silylated forms using activated alkyl halides or acetates in the presence of Lewis acids.In the case of unsymmetricall
