A supramolecularly tunable chiral diphosphine ligand: application to Rh and Ir-catalyzed enantioselective hydrogenation.

A supramolecularly tunable chiral bisphosphine ligand bearing two pyridyl-containing crown ethers, (-) or (+)-Xyl-P16C6-Phos, was fabricated and utilized in the Rh-catalyzed asymmetric hydrogenation of α-dehydroamino acid esters and Ir-catalyzed asymmetric hydrogenation of quinolines in high yields with excellent enantioselectivities (90-99% ee). Up to a 22% enhancement in enantioselectivity was achieved by the addition of certain amounts of alkali ions (Li+, Na+ or K+), which could be selectively recognized and effectively complexed by the crown ethers on the chiral Xyl-P16C6-Phos.

Microbial degradation of alpha-cypermethrin in soil by compound-specific stable isotope analysis.

To assess microbial degradation of alpha-cypermethrin in soil, attenuation of alpha-cypermethrin was investigated by compound-specific stable isotope analysis. The variations of the residual concentrations and stable carbon isotope ratios of alpha-cypermethrin were detected in unsterilized and sterilized soils spiked with alpha-cypermethrin. After an 80 days' incubation, the concentrations of alpha-cypermethrin decreased to 0.47 and 3.41 mg/kg in the unsterilized soils spiked with 2 and 10 mg/kg, while those decreased to 1.43 and 6.61 mg/kg in the sterilized soils. Meanwhile, the carbon isotope ratios shifted to -29.14 ± 0.22‰ and -29.86 ± 0.33‰ in the unsterilized soils spiked with 2 and 10 mg/kg, respectively. The results revealed that microbial degradation contributed to the attenuation of alpha-cypermethrin and induced the carbon isotope fractionation. In order to quantitatively assess microbial degradation, a relationship between carbon isotope ratios and residual concentrations of alpha-cypermethrin was established according to Rayleigh equation. An enrichment factor, ϵ = -1.87‰ was obtained, which can be employed to assess microbial degradation of alpha-cypermethrin. The significant carbon isotope fractionation during microbial degradation suggests that CSIA is a proper approach to qualitatively detect and quantitatively assess the biodegradation during attenuation process of alpha-cypermethrin in the field.

Copper-dipyridylphosphine-catalyzed hydrosilylation: enantioselective synthesis of aryl- and heteroaryl cycloalkyl alcohols.

The non-precious metal copper-catalyzed enantioselective hydrosilylation of a vast array of aryl cycloalkyl ketones with different ring sizes was studied systematically for the first time (up to 99% enantiomeric excess). The results demonstrated that the steric size of cycloalkyl groups has a significant influence on the reaction outcomes. The first stereoselective formation of a selection of cyclohexyl heteroaryl alcohols of up to 97% enantiopurity was realized as well. Dramatic temperature effects on both the enantiopurity and the absolute configuration of the alcohol products were observed in the reduction of some cyclohexyl pyridyl ketones.

Nickel(II)-dipyridylphosphine-catalyzed enantioselective hydrosilylation of ketones in air.

Out of thin air: Catalytic amounts of nickel(II) salt and non-racemic dipyridylphosphine ligand, as well as the stoichiometric hydride source PhSiH(3), formed an effective catalyst system for the Ni(II)-catalyzed asymmetric hydrosilylation of a diverse range of electron-deficient aryl alkyl ketones with enantioselectivities up to 90% ee. The practical potential of the protocol was evinced by its good air-stability.

Cu(II)-catalyzed asymmetric hydrosilylation of diaryl- and aryl heteroaryl ketones: application in the enantioselective synthesis of orphenadrine and neobenodine.

With certain amounts of sodium tert-butoxide and tert-butanol as additives, catalytic amounts of an inexpensive and easy-to-handle copper source Cu(OAc)(2)⋅H(2)O, a commercially available and air-stable non-racemic dipyridylphosphine ligand, as well as the stoichiometric desirable hydride donor polymethylhydrosiloxane (PMHS), formed a versatile in situ catalyst system for the enantioselective reduction of a broad spectrum of prochiral diaryl and aryl heteroarylketones in air, in high yields and with good to excellent enantioselectivities (up to 96 %). In particular, the practical viability of this process was evinced by its successful applications in the asymmetric synthesis of optically enriched potent antihistaminic drugs orphenadrine and neobenodine.

Copper(II)-catalyzed hydrosilylation of ketones using chiral dipyridylphosphane ligands: highly enantioselective synthesis of valuable alcohols.

In the presence of PhSiH(3) as the reductant, the combination of enantiomeric dipyridylphosphane ligands and Cu(OAc)(2)·H(2)O, which is an easy-to-handle and inexpensive copper salt, led to a remarkably practical and versatile chiral catalyst system. The stereoselective formation of a selection of synthetically interesting ß-, γ- or δ-halo alcohols bearing high degrees of enantiopurity (up to 99.9% enantiomeric excess (ee)) was realized with a substrate-to-ligand molar ratio (S/L) of up to 10,000. The present protocol also allowed the hydrosilylation of a diverse spectrum of alkyl aryl ketones with excellent enantioselectivities (up to 98% ee) and exceedingly high turn-over rates (up to 50,000 S/L molar ratio in 50 min reaction time) in air, under very mild conditions, which offers great opportunities for the preparation of various physiologically active targets. The synthetic utility of the chiral products obtained was highlighted by the efficient conversion of optically enriched ß-halo alcohols into the corresponding styrene oxide, ß-amino alcohol, and ß-azido alcohol, respectively.

Cobalt(II)-catalyzed asymmetric hydrosilylation of simple ketones using dipyridylphosphine ligands in air.

In the presence of PhSiH(3) as the hydride donor, catalytic amounts of non-racemic dipyridylphosphine and an easy-to-handle cobalt salt Co(OAc)(2)·4H(2)O formed in situ an effective catalyst system for the asymmetric reduction of a diverse range of aryl alkyl ketones with moderate-to-excellent enantioselectivities (up to 96% ee). This approach tolerated the handling of both catalyst and reactants under air without special precautions.

Synthesis of ß-amino acid derivatives via copper-catalyzed asymmetric 1,4-reduction of ß-(acylamino)acrylates.

A new set of reaction conditions has been established to facilitate the copper-catalyzed enantioselective 1,4-reduction of ß-(acylamino)acrylates toward a selection of ß-alkyl-ß-amino acid derivatives in high yields and with uniformly high ee values (up to 99%) irrespective of the use of (E)- or (Z)-substrates.

Application of copper(II)-dipyridylphosphine catalyst in the asymmetric hydrosilylation of simple ketones in air.

Ask a copper: A copper(II) salt/chiral dipyridylphosphine/PhSiH(3) system (see scheme) acts as a very effective and practical catalyst for the asymmetric reduction of heteroaromatic and other types of ketones in air with good-to-excellent enantioselectivities (up to 94%), giving many chiral alcohols that are intermediates for physiologically active compounds. Remarkable temperature effects were observed for some heteroaromatic ketones.