154669-86-0Relevant academic research and scientific papers
Visible-Spectrum Solar-Light-Mediated Benzylic C-H Oxygenation Using 9,10-Dibromoanthracene As an Initiator
Santra, Sourav K.,Szpilman, Alex M.
, p. 1164 - 1171 (2020/12/23)
We report a visible-light-mediated benzylic C-H oxygenation reaction. The reaction is initiated by solar light or the blue LED activation of 9,10-dibromoanthracene in a reaction with oxygen and takes place at ambient temperature and air pressure. Secondary benzylic positions are oxygenated to ketones, while tertiary benzylic carbons are oxygenated to give hydroperoxides. Notably, cumene hydroperoxide is produced in a higher yield and at milder conditions than the currently employed industrial conditions.
Functionalization of amides via copper-catalyzed oxyalkylation of vinylarenes and decarboxylative alkenylation of sp3 C-H
Yan, Hong,Lu, Linhua,Rong, Guangwei,Liu, Defu,Zheng, Yang,Chen, Jie,Mao, Jincheng
, p. 7103 - 7111 (2014/08/18)
An efficient protocol was developed to prepare a series of derivatives from amides by copper-catalyzed oxyalkylation of vinylarenes and decarboxylative alkenylation of sp3 C-H. This method is simple, practical, and inexpensive.
The palladium-catalyzed aerobic kinetic resolution of secondary alcohols: Reaction development, scope, and applications
Ebner, David C.,Bagdanoff, Jeffrey T.,Ferreira, Eric M.,McFadden, Ryan M.,Caspi, Daniel D.,Trend, Raissa M.,Stoltz, Brian M.
supporting information; experimental part, p. 12978 - 12992 (2010/06/19)
The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23°C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-toexcellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.
The resolution of important pharmaceutical building blocks by palladium-catalyzed aerobic oxidation of secondary alcohols
Caspi, Daniel D.,Ebner, David C.,Bagdanoff, Jeffrey T.,Stoltz, Brian M.
, p. 185 - 189 (2007/10/03)
The palladium-catalyzed aerobic oxidative kinetic resolution of key pharmaceutical building blocks is described. Substrates investigated are relevant to the enantioselective preparation of Prozac, Singulair, and the promising hNK-1 receptor antagonist from Merck. The latter provides the most selective aerobic oxidative kinetic resolution yet described.
Palladium-catalyzed synthesis of aryl ketones from boronic acids and carboxylic acids activated in situ by pivalic anhydride
Goossen, Lukas J.,Ghosh, Keya
, p. 3254 - 3267 (2007/10/03)
A new palladium-catalyzed cross-coupling reaction between arylboronic acids and mixed anhydrides, generated in situ from carboxylic acids and pivalic anhydride, is presented. Optimization of the new catalyst and the reaction conditions led to the development of a convenient one-pot ketone synthesis directly from carboxylic and boronic acids in the presence of different (phosphane)palladium complexes in wet THF at 60 °C. Systematic studies were performed to elucidate the reaction mechanism of this transformation. The scope and the limitations of the new process are demonstrated by the synthesis of 33 functionalized ketones. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
Preparation and reactivity of chiral β-amino-alkylzinc iodides and related configurationally stable zinc organometallics
Duddu,Eckhardt,Furlong,Knoess,Berger,Knochel
, p. 2415 - 2432 (2007/10/02)
Several zinc organometallics bearing at the β-position a carbamate or an amido function with an acidic N-H group were prepared using the direct insertion of zinc dust into the corresponding alkyl iodides in THF or THF:DMSO mixtures. Most of the starting iodides were obtained from natural α-amino acids and the resulting zinc species afforded after transmetalation with CuCN.2LiCl and reaction with a selection of relatively reactive electrophiles a variety of polyfunctional 1,2-amino alcohol derivatives and carbamates in optically pure form. Several secondary β-amido alkyl iodides were converted to the corresponding chiral zinc reagents and trapped with electrophiles. The configurational stability of chiral secondary organozinc compounds and the stereochemical course of their reactions were examined.
