Divergent Synthesis of Natural Benzyl Salicylate and Benzyl Gentisate Glucosides.

Herein is reported the first total synthesis of benzyl salicylate and benzyl gentisate glucosides present in various plant species, in particular the genus, such as and . The method permits the synthesis of several natural phenolic acid derivatives and their glucosides starting from salicylic or gentisic acid. The divergent approach afforded access to three different acetylated glucosides from a common synthetic intermediate.

Synthesis of Acetyl Salicins Using Selective Deacetylation and Acetyl Group Migration.

In the present work, the synthesis of acetylated salicins, which occur naturally in many species, is reported. The preparation of 2--acetylsalicin, 2--acetylchlorosalicin, and 2--acetylethylsalicin from peracetylated bromosalicin with selective acid-catalyzed deacetylation and one-pot nucleophilic substitution of bromine as the key steps is described. The base-catalyzed O-2 → O-6 acetyl migration afforded 6--acetylsalicin derivatives in good yields.

Synthesis, biological evaluation, and molecular modeling of 11H-indeno[1,2-b]quinoxalin-11-one derivatives and tryptanthrin-6-oxime as c-Jun N-terminal kinase inhibitors.

c-Jun N-terminal kinases (JNKs) play a central role in many physiologic and pathologic processes. We synthesized novel 11H-indeno[1,2-b]quinoxalin-11-one oxime analogs and tryptanthrin-6-oxime (indolo[2,1-b]quinazoline-6,12-dion-6-oxime) and evaluated their effects on JNK activity. Several compounds exhibited sub-micromolar JNK binding affinity and were selective for JNK1/JNK3 versus JNK2.

A new look at acid catalyzed deacetylation of carbohydrates: A regioselective synthesis and reactivity of 2-O-acetyl aryl glycopyranosides.

In the present work we report that acetyl groups of per - acetylated aryl glycosides have different reactivity during the acidic deacetylation using HCl/EtOH in CHCl which leads to preferential deacetylation at O-3, O-4 and O-6. Thereby, the one-step preparation of 2-O-acetyl aryl glycosides with simple aglycon was accomplished for the first time. It was proved that the found reagent is to be general and unique for the preparation of series of 2-О-acetyl aryl glycosides.

The first example of a one-step synthesis of 2'-O-acetyl aryl-D-glucopyranosides.

A selective acidic system for partial deacetylation of phenolic d-glucopyranosides per-acetates has been developed that allows synthesis of the corresponding 2'-O-acetyl-D-glucosides. Many disadvantages of generally used methods for preparing such mono-acyl derivatives involving multistep procedures or the use of enzymes are avoided. The ion at m/z 289 in mass spectra of their TMS derivatives indicates a particular and characteristic fragmentation pattern of these 2'-O-acetyl derivatives of d-glucopyranosides.

Synthesis of acyl derivatives of salicin, salirepin, and arbutin.

The total synthesis of two natural phenolglycosides of the family Salicaceae, namely: populoside and 2-(β-d-glucopyranosyloxy)-5-hydroxy benzyl (3-methoxy-4-hydroxy) cinnamoate and nine not found yet in plants acyl derivatives of phenoglycosides: 2-(β-d-glucopyranosyloxy)-benzylcinnamoate, 2-(β-d-glucopyranosyloxy)-benzyl (4-hydroxy) benzoate, 2-(β-d-glucopyranosyloxy)-benzyl (3-methoxy-4-hydroxy) benzoate, 2-(β-d-glucopyranosyloxy)-5-hydroxy benzyl (3,4-dihydroxy) cinnamoate, 2-(β-d-glucopyranosyloxy)-5-hydroxy benzylcinnamoate, 2-(β-d-glucopyranosyloxy)-5-hydroxy benzyl (4-hydroxy) benzoate, 2-(β-d-glucopyranosyloxy)-5-hydroxy benzyl (3-methoxy-4-hydroxy) benzoate, 2-(β-d-glucopyranosyloxy)-5-benzoyloxy benzylbenzoate and 4-(β-d-glucopyranosyloxy)-phenylbenzoate, starting from readily available phenols and glucose was developed for the first time.

First total chemical synthesis of natural acyl derivatives of some phenolglycosides of the family Salicaceae.

The total synthesis of certain natural phenolglycosides of the family Salicaceae, namely: salireposide, populosides A, B, and C and not occurring in plants desoxysalireposide (2-(β-D-glucopyranosyloxy)-benzylbenzoate) and per-acetate of iso-salireposide (2-(β-D-glucopyranosyloxy)-5-benzoyloxy benzyl alcohol), starting from readily available phenols and glucose was accomplished. A simple method for the synthesis of phenolglycosides derivatives of 2-acyloxy salicyl and gentisyl alcohol was developed. The key step of these natural products' synthesis is a selective removal of acetyl groups in the presence of other acyl groups.