Biomaterials from sugars: ring-opening polymerization of a carbohydrate lactone

Polymers from sugars: cyclic monomer synthesis, ring-opening polymerisation, material properties and applications

“…NOESY NMR experiments suggested that the boat conformation adopted by the carbohydrate ring in the X-ray crystal structure is maintained in solution. 85 Synthesis of 1,6-lactones from carbohydrates requires more elaborate synthetic sequences and protecting group chemistry. O-Methyl protected D-glucono-1,6-lactone 23 was prepared by Galbis and coworkers via lactonisation of an o-hydroxyacid intermediate, using dicyclohexylcarbodiimide (DCC) and 4-(dimethylamino)pyridine (DMAP) in the presence of DMAPÁHCl (Fig.…”

Monomers and Macromonomers from Renewable Resources

“…This interesting investigation has been extended to include aliphatic biodegradable polyurethanes bearing L -arabinitol and 2,2 ' -dithiodiethanol [23] . Furthermore, the preparation of a novel carbohydrate lactone and its ring -opening polymerization were shown to yield a functionalized cyclic aliphatic polyester [24] . A very thorough study of the synthesis of sugar monoisocyanates [25] , aimed at preparing ureido -linked disaccharides, should inspire polymer chemists to extend it to diisocyanate homologs.…”

“…24 The epoxydation of methyl linolenate by performic acid 25. Hydroxylated and acrylated derivative of epoxidized soy oil.…”

Ring‐Opening Metathesis Polymerization of Biomass‐Derived Levoglucosenol

“…[2] Another important chemical that can be readily obtained from cellulose is 1,6-anhydro-3,4dideoxy-D 3 -b-d-pyranosen-2-one (IUPAC name:(1S,5R) -6,8dioxabicyclo[3.2.1]oct-2-en-4-one),a lso known as levoglucosenone. [8] Pure levoglucosenone (1;w hich is also commercially available,s ee the Supporting Information) was readily obtained from the acid-catalyzed pyrolysis of cellulose (Scheme 1). To the best of our knowledge,this is the first example of asuccessful metathesis polymerization of ap urely sugar-derived monomer.S ugarrelated systems described so far include natural macrocyclic glycolipids,w hich are polymerized via the unsaturated fatty acid part, [6] or saccharides attached to an orbornene or 7oxanorbornene scaffold.…”

“…[7] Additionally,astructurally related carbohydrate lactone derived from gluconolactone was polymerized by ROP using atin-based catalyst to yield low molar mass polyesters. [8] Pure levoglucosenone (1;w hich is also commercially available,s ee the Supporting Information) was readily obtained from the acid-catalyzed pyrolysis of cellulose (Scheme 1). [1] Thea ttempts of free-radical or anionic polymerization of 1 with azobisisobutyronitrile( AIBN) or secbutyl lithium (sBuLi)a si nitiators,r espectively,w ere not successful, producing low-molar-mass oligomeric materials only (data not shown).…”