Highly enantioselective resolution of terminal epoxides with cross-linked polymeric salen-Co(III) complexes

Crosslinked polymeric salen-Co(III) complexes derived from a novel dialdehyde and a trialdehyde were synthesized and employed in the hydrolytic kinetic resolution (HKR) of terminal epoxides. Up to 99%, ee were obtained with only 0.16-0.02 mol%,, of catalyst (based on catalytic unit). (C) 2003 Elsevier Ltd. All rights reserved.

Cyclopropanation on a highly active heterogeneous catalyst: CuO/TiO2-Al2O3

Some heterogeneous catalysts, cupric oxide supported on different supports, were prepared and employed to catalyze the cyclopropanation of styrene and 2,5-dimethyl-2,4-hexadiene with ethyl diazoacetate (EDA). The catalytic performance for cyclopropanation strongly depends on the nature of the support. A novel catalyst, CUO/TiO2-Al2O3, in which Al2O3 is modified with a monolayer TiO2, is found to be most active and selective for the cyclopropanation reaction. The yields of 93 and 94% cyclopropanes are obtained for styrene and 2,5-dimethyl-2,4-hexadiene at 40 degreesC as the substrates, respectively. The activity and selectivity in cyclopropanes are optimized with a monolayer dispersion of cupric oxide on the corresponding supports. (C) 2002 Elsevier Science B.V. All rights reserved.

Asymmetric cyclopropanation of styrene catalyzed by Cu-(chiral Schiff-base) complexes

Asymmetric cyclopropanation of olefins was carried out with chiral copper-Schiff base complexes derived from copper acetate monohydrate, substituted salicylaldehydes and a chiral amino alcohol. Substituents on salicylaldehyde framework demonstrate a significant effect on the steroselectivities. Those with electron-withdrawing properties enhance the selectivities, whereas bulky sustituents in ortho position to the phenol hydroxy group decrease the selectivities. An ee of more than 98% was achieved for the reaction of styrene with diazoacetate. (C) 2000 Elsevier Science Ltd. All rights reserved.

Synthesis, characterization and catalytic properties of chiral BINOL functionalized mesoporous silicas for enantioselective Morita-Baylis-Hillman reaction

Several Chiral BINOL functionalized mesoporous silicas were prepared by post grafting of organosilane derivatives of (S)-BINOL (1,1'-bi-2-naphthol) on SBA-15 and characterized by C-13 CP/MAS NMR, FT-IR, UV-visible absorption spectra, elemental analysis, powder XRD, nitrogen adsorption-desorption isotherms and TEM techniques. Their catalytic properties were demonstrated in enantioselective Morita-Baylis-Hillman reaction of 3-phenylpropanal and cyclohexenone.

Enantioselective Iodolactonizations of 4-Pentenoic Acid Derivatives Mediated by Chiral Salen-Co(II) Complex

This work presents the salen-Co(II) complex catalyzed enantioselective iodolactonizations of various 4-pentenoic acid derivatives with good enantioselectivities (up to 83% ee).

(R,R)-DPEN-modified Ru/gamma-Al2O3 - An efficient heterogeneous catalyst for enantioselective hydrogenation of acetophenone

An efficient enantioselective catalyst of 5 wt.% Ru/-gamma-Al2O3 modified with R,R-1,2-diphenylethylene-diamine ((R,R)-DPEN) for the hydrogenation of a non-activated aromatic ketone of acetophenone has been investigated, a relatively high enantiomeric excess (ee) of 60.5% was obtained at both the conversion and selectivity larger than 99%, it was about three times higher than the ee values reported up to now for acetophenone hydrogenation with the supported transition metal catalysts modified by chiral reagents. The influences of some reaction parameters such as phosphine ligand, substrate/catalyst/modifier molar ratios, base, solvent, pressure and reaction temperature have been discussed. The chiral modifier of (R,R)-DPEN was very important in controlling the enantioselectivity through adsorption competing with other substrates on the surface of active metal species. The phosphine ligand and base were also important and indispensable in the present reaction.

Enantioselective iodolactonization catalyzed by chiral quaternary ammonium salts derived from cinchonidine

Chiral quaternary ammonium salts derived from cinchonidine have been applied to catalyze the stereoselective iodolactonizations of trans-5-aryl-4-pentenoic acids leading to a mixture of two regioselectively iodolactonized products with fair to excellent yield (37-98%) and moderate enantioselectivity (exo = 42.0% ee, endo = 31.0% ee) under mild conditions. This work is the first example of asymmetric iodolactonization reaction in the presence of less than a stoichiometric amount of chiral reagent.

Highly enantioselective resolution of terminal epoxides using polymeric catalysts

Poly-salen-Co(III) complexes were employed in the hydrolytic kinetic resolution (HKR) of terminal epoxides and ee's up to 98% were obtained. In the HKR of epichlorohydrin, the polymeric catalysts can be recovered and modified for recycling. The recovered polymer catalyst shows good activity and selectivity. (C) 2002 Elsevier Science Ltd. All rights reserved.