19141-39-0Relevant articles and documents
Empirical method for predicting enantioselectivity in catalytic reactions: demonstration with lipase and oxazaborolidine
Ema, Tadashi,Ura, Norichika,Yoshii, Masataka,Korenaga, Toshinobu,Sakai, Takashi
supporting information; experimental part, p. 9583 - 9591 (2010/01/06)
We derived a novel equation capable of predicting the degree of enantioselectivity in a catalytic reaction without any knowledge of the reaction mechanism and/or the transition-state structure, and tested the validity of this equation by changing substrates systematically in the lipase or oxazaborolidine-catalyzed reactions. A good correlation was observed between the predicted and observed E values, and the stereochemistry of the products could be predicted correctly in most cases (28 out of 30).
Generation of a solid Bronsted acid site in a chiral framework
Ingleson, Michael J.,Barrio, Jorge Perez,Bacsa, John,Dickinson, Calum,Park, Hyunsoo,Rosseinsky, Matthew J.
, p. 1287 - 1289 (2008/12/21)
Protonation of chiral porous materials introduces a Bronsted acid centre, the structure of which is unique to the heterogeneous phase requiring pore wall confinement for stable isolation. The Royal Society of Chemistry.
A new dinuclear chiral salen complexes for asymmetric ring opening and closing reactions: Synthesis of valuable chiral intermediates
Thakur, Santosh Singh,Chen, Shu-Wei,Li, Wenji,Shin, Chang-Kyo,Kim, Seong-Jin,Koo, Yoon-Mo,Kim, Geon-Joong
, p. 1862 - 1872 (2007/10/03)
A new dinuclear chiral Co(salen) complexes bearing group 13 metals have been synthesized and characterized. The easily prepared complexes exhibited very high catalytic reactivity and enantioselectivity for the asymmetric ring opening of epoxides with H2O, chloride ions and carboxylic acids and consequently provide enantiomerically enriched terminal epoxides (>99% ee). It also catalyzes the asymmetric cyclization of ring opened product, to prepare optically pure terminal epoxides in one step. The homogeneous dinuclear chiral Co(salen) have been covalently immobilized on MCM-41. The potential benefits of heterogenization include facilitation of catalyst separation and recyclability requiring very simple techniques. The system described is very efficient.
Highly reactive and enantioselective kinetic resolution of terminal epoxides with H2O and HCl catalyzed by new chiral (salen)Co complex linked with Al
Thakur, Santosh Singh,Li, Wenji,Kim, Seong-Jin,Kim, Geon-Joong
, p. 2263 - 2266 (2007/10/03)
The asymmetric hydrolytic kinetic resolution (HKR) of racemic terminal epoxides by new easily synthesized dimeric chiral (salen)Co bearing Al, provides a practical and straightforward method for the synthesis of enantiomerically enriched terminal epoxides (>99% ee) and diols. An inorganic acid, HCl is applied first time for the asymmetric ring opening reaction of terminal epoxides. Reactions are conveniently carried out at room temperature under an air atmosphere.
The effect of catechin derivatives on the enantioselectivity of lipase-catalyzed hydrolyses of alkynol benzoate esters
Nakamura, Kaoru,Takenaka, Keishi
, p. 415 - 422 (2007/10/03)
Polyphenols, such as (+)-catechin and pyrogallol could be used to enhance stereochemical control in the lipase-catalyzed hydrolysis of alkynol benzoate esters, leading to increased enantioselectivities in the kinetic resolution of alkynols with lipase Amano AH.
Oxidation of olefins by palladium(II): Part 17. An asymmetric chlorohydrin synthesis catalyzed by a bimetallic palladium(II) complex
El-Qisairi, Arab,Henry, Patrick M.
, p. 50 - 60 (2007/10/03)
Previous studies showed that oxidation of α-olefins with monometallic catalysts containing chiral diphosphines and diamines gave chlorohydrins with poor to good enantioselectivites (28-82% ee). The present studies demonstrate that bimetallic catalysts containing a β-triketone and bridging chiral diphosphine and diamines are excellent catalysts for this reaction giving enantioselectivites considerably higher than the monometallic catalysts. Enantioselectivities were more than 50% for most olefins tested. The highest optical purities were 94% ee for propene and 93% ee for allylphenyl ether. A useful feature of this asymmetric synthesis is the fact it is a net air oxidation.
Enantiomerically enriched bifunctional sec-alcohols prepared by Candida antarctica lipase B catalysis. Evidence of non-steric interactions
Rotticci, Didier,Orrenius, Christian,Hult, Karl,Norin, Torbjoem
, p. 359 - 362 (2007/10/03)
Transesterification catalysed by Candida antarctica lipase B was used for the preparation of enantiomerically enriched bifunctional sec-alcohols. The enantiomeric ratio, E, for 3-butyn-2-ol was increased from 1.3 to over 500 by adding an easily removable protecting group. Kinetic resolution of bromohydrins and chlorohydrins bearing a halogen on the large substituent showed high enantioselectivity (E >80). On the other hand, halohydrins with the halogen on the medium group showed low E. Large differences in enantioselectivity were found by substituting the halogen atom of 1-halo-2-alkanols by a methyl group. These differences corresponded to more than 2 kcal mol-1 and were ascribed to non-steric interactions.
ASSYMETRIC REDUCTION OF KETONES BY GLYCEROL DEHYDROGENASE FROM GEOTRICUM
Nakamura, Kaoru,Yoneda, Tetsuo,Miyai, Takehiko,Ushio, Kazutoshi,Oka, Shinzaburo,Ohno, Atsuyoshi
, p. 2453 - 2454 (2007/10/02)
Glycerol dehydrogenase from Geotricum was used as a catalyst for asymmetric reduction of ketones.A 2-propanol-NAD couple was employed to supply NADH.