1197922-04-5Relevant articles and documents
A base-free neutral phase-transfer reaction system
Shirakawa, Seiji,Wang, Lijia,He, Rongjun,Arimitsu, Satoru,Maruoka, Keiji
supporting information, p. 1586 - 1593 (2014/06/09)
Although phase-transfer reactions catalyzed by using quaternary ammonium salts are generally believed to require base additives, we discovered that, even without any base additives, conjugate additions of 3-substituted oxindoles to nitroolefins proceeded smoothly in the presence of lipophilic quaternary ammonium bromide under water-organic biphasic conditions. The mechanism of this novel base-free neutral phase-transfer reaction system is investigated and the assumed catalytic cycle is presented together with interesting effects of water and lipophilicity of the phase-transfer catalyst. The base-free neutral phase-transfer reaction system can be applied to highly enantioselective conjugate addition and aldol reactions under the influence of chiral bifunctional ammonium bromides as key catalysts. The structure of the chiral ammonium enolate intermediate is discussed based on the single-crystal X-ray structures of relevant ammonium salts and the importance of bifunctional design of catalyst is clearly explained in the model of intermediate. In and out of phase: The mechanism of a novel base-free neutral phase-transfer reaction system was investigated (see scheme). The aqueous-organic biphasic reaction system with lipophilic tetraalkylammonium bromide was essential to promote the neutral phase-transfer reactions. The base-free reaction system could be applied to several asymmetric reactions.
Enantioselective base-free phase-transfer reaction in water-rich solvent
He, Rongjun,Shirakawa, Seiji,Maruoka, Keiji
supporting information; experimental part, p. 16620 - 16621 (2010/02/15)
(Chemical Equation Presented) The development of enantioselective phase-transfer catalysis for preparing important natural products or physiologically active compounds is quite attractive and challenging in terms of environmental consciousness. Although q