Efficient synthesis of alkyl 2,3-unsaturated glucopyranosides from glycals mediated by ytterbium(III) triflate-trialkyl aluminum

Treatment of glycals with trialkylaluminum in the presence of a catalytic amount of Yb(OTf)₃ leads to the corresponding alkyl 2,3-unsaturated glycosides in good to excellent yields. Reactions of protected glycals are achieved under very mild conditions.     

One-step purification of palmatine and its derivative dl-tetrahydropalmatine from Enantia chlorantha using high-performance displacement chromatography

Palmatine and its reduced form, dl-tetrahydropalmatine are a group of isoquinoline alkaloids that have been reported to display a variety of biological and pharmacological activities. Both drugs are hydrophilic and are difficult to be purified by conventional purification methods of natural products. A high-performance displacement chromatography (HPDC) method successfully purified palmatine and its semi-synthetic derivative dl-tetrahydropalmatine from crude extract of the African medicinal plant Enantia chlorantha. The crude extract from the root bark of E. chlorantha was fractionated on an analytical reversed-phase C(18) column by using 0.1% trifluoroacetic acid (TFA) or acetic acid/H2O as a carrier and cetylpyridinium trifluoroacetate (or acetate) (1.9mg/mL) in 0.1% TFA (or acetic acid)/H2O as a displacer. Palmatine was quantitatively purified at >98% purity in the fully developed displacement mode. dl-Tetrahydropalmatine was semi-synthesized by NaBH4 reduction from crude palmatine and directly purified by HPDC. Both palmatine and dl-tetrahydropalmatine were identified by high-resolution electrospray tandem mass spectrometry, (1)H NMR and (13)C NMR. This is the first report of one-step HPDC purification of natural and semi-synthetic products from a complex crude extract.     

α,α-Difluoro-α-phenylsulfanylmethyl carbanion equivalent: a novel gem-difluoromethylenation of carbonyl compounds

α,α-Difluoro-α-phenylsulfanyl-α-trimethylsilylmethane (PhSCF₂SiMe₃) has been demonstrated as an α,α-difluoro-α-phenylsulfanylmethyl carbanion equivalent. gem-Difluorophenylsulfanylmethylation of carbonyl compounds has been successfully achieved by using PhSCF₂SiMe₃ in the presence of TBAF in THF. The adducts have been converted to the corresponding gem-difluoroalkenes by a novel pyrolytic and/or FVP elimination of the β-hydroxy-α-phenylsufinyl derivatives under reduced pressure.