Selective Modification of Aliphatic Hydroxy Groups in Lignin Using Ionic Liquid

A facile, sustainable method for the selective modification of aliphatic hydroxy (R–OH) groups in Kraft lignin was developed using an ionic liquid, 1-ethyl-3-methylimidazolium acetate (EmimOAc), as a solvent and catalyst. Selective R–OH modification was achieved by a one-pot, two-step homogeneous reaction: (i) acetylation of R–OH and aromatic OH (Ar–OH) groups with isopropenyl acetate (IPAc) as an acyl donor and (ii) subsequent selective deacetylation of the generated aromatic acetyl (Ar–OAc) groups. In step (i), IPAc reacts rapidly with Ar–OH but slowly with R–OH. The generated Ar–OAc is gradually deacetylated by heating in EmimOAc, whereas the aliphatic acetyl (R–OAc) groups are chemically stable. In step (ii), all R–OH is acetylated by IPAc and Ar–OAc which is a better acyl donor than IPAc, contributing to the rapid acetylation of the remaining R–OH, and selective deacetylation of the residual Ar–OAc is completed by adding a tiny amount of water as a proton source. This two-step reaction resulted in selective R–OH modification (>99%) in Kraft lignin with the remaining being almost all Ar–OH groups (93%). Selectively modified Kraft lignin was obtained with an acceptably high isolated yield (85%) and repeatability (N = 3). Furthermore, despite the lower substitution degree, it exhibited solubility in common solvents, heat-meltability, and thermal stability comparable to completely acetylated Kraft lignin.

Synthesis of 3′-azido/-amino-xylobicyclonucleosides

Lipozyme® TL IM mediated the selective deacetylation of one of the two acetoxy groups in 4-C-acetoxymethyl-5-O-acetyl-3-azido-3-deoxy-1,2-O-isopropylidene-α-d-xylofuranose, leading to the first efficient syntheses of 3′-azido/3′-amino-xylobicyclonucleosides T, U, C and A.

Selective methylation of kaempferol via benzylation and deacetylation of kaempferol acetates

A strategy for selective mono-, di- and tri-O-methylation of kaempferol, predominantly on the basis of selective benzylation and controllable deacetylation of kaempferol acetates, was developed. From the selective deacetylation and benzylation of kaempferol tetraacetate (1), 3,4′,5,-tri-O-acetylkaempferol (2) and 7-O-benzyl-3,4′5,-tri-O-acetylkaempferol (8) were obtained, respectively. By controllable deacetylation and followed selective or direct methylation of these two intermediates, eight O-methylated kaempferols were prepared with 51–77% total yields from kaempferol.