•Hf(OTf)4 was used efficient catalyst for Type I Ferrier Rearrangement to achieve 2,3-unsaturated N- and C-pseudoglycosides.•Three kinds of glycals were used as substrates to get the corresponding glycols.•The reaction could proceed smoothly at low reaction temperature.By using Hf(OTf)4 as the catalyst, a series of 2,3-N- and C-unsaturated-glucosides have been synthesized from 3,4,6-tri-O-acetyl-d-glucal, 2,4,6-tri-O-benzyl-d-glucal and ((2R,3S)-3-acetoxy-2,3-dihydrofuran-2-yl)methyl acetate under mild reaction conditions in good yields with high anomeric selectivities.

By using Gd(OTf)3 as the catalyst, synthesis of 2,3-unsaturated-glycosides has been performed by Ferrier Rearrangement. A series of 2,3-unsaturated O-, S-, N-, and C-glycosides were obtained from 3,4,6-tri-O-acetyl-d-glucal, 3,4,6-tri-O-benzyl-d-glucal, and 3,4-di-O-acetyl-l-rhamnal under mild reaction conditions in good yields and high anomeric selectivities.

•Tm(OTf)3 was used as a new catalyst for Ferrier Rearrangement.•Two kinds of glycals were used as substrates to react with nucleophiles.•O-, S-, N- or C-2,3-unsaturated glycosides were prepared efficiently.By using Tm(OTf)3 as the catalyst, an efficient Ferrier Rearrangement reaction system has been established. A series of O-, S-, N-, and C-2, 3-unsaturated-glucosides were obtained in good yields and high anomeric selectivities by the glycosidation of 3,4,6-tri-O-acetyl-d-glucal or 3,4-di-O-acetyl-l-rhamnal with the corresponding nucleophiles, including azaglycosylation with N-nucleophiles.

By using lipase PS-30 as catalyst, the kinetic resolution of a series of racemic mandelate esters has been achieved via stereoselective acylation. The value of kinetic enantiomeric ratio (E) reached up to 197.5. Substituent effect is briefly discussed.Seventeen examples. Values of the kinetic enantiomeric ratio (E) up to 197.5.

•Y(OTf)3 was used as a new, efficient catalyst for Type I Ferrier Rearrangement.•Three kinds of glycals were used as substrates to react with O- or S-nucleophiles.•Tri-benzyl-glucal reacted with PhOH to form 1-BnO glucoside as the sole product.By using Y(OTf)3 as the catalyst, a series of 2,3-unsaturated-glucosides have been synthesized from 3,4,6-tri-O-acetyl-d-glucal, 3,4-di-O-acetyl-l-rhamnal, and 3,4,6-tri-O-benzyl-d-glucal under mild reaction conditions in good yields with high anomeric selectivities. It was found that, in this reaction, 3,4,6-tri-O-benzyl-d-glucal behaved differently from the other two glucals when it was reacted with phenol, O-benzyl glucoside instead of O-phenyl glucoside formed as the sole product. An explanation is given for this phenomenon.

By using lipase PS-30 as catalyst, the kinetic resolution of a series of racemic allylic alcohols has been achieved via stereoselective acylation. The value of kinetic enantiomeric ratio (E) reached up to 968. Substituent effect is briefly discussed.Eleven examples. Values of the kinetic enantiomeric ratio (E) up to 968.

By using lipase PS-30 as catalyst, the kinetic resolution of a series of racemic propargylic alcohols has been achieved via stereoselective acylation. The value of kinetic enantiomeric ratio (E) reached up to 139. Substituent effect is briefly discussed.Fourteen examples. Values of the kinetic enantiomeric ratio (E) up to 139.Download full-size image