Isohexide Derivatives from Renewable Resources as Chiral Building Blocks

Abstract

Hextended family: A new family of C2/C5 carbon‐extended isohexide derivatives is synthesized in a stereo‐controlled manner with high purity and good yield. These chiral and rigid biobased building blocks can be widely applied: in pharmaceuticals, cholesteric liquid crystals, and as building blocks for high‐performance polymers. The isoidide‐based diacid is a potential renewable alternative to terephthalic acid.

Isohexide and Sorbitol-Derived, Enzymatically Synthesized Renewable Polyesters with Enhanced Tg

“…18,19 In previous studies related to polymers derived from unmodified OH-functional isohexides, lower thermal stability has been observed for the endo-substituted isohexide-containing polymers. Isoidide showed to be the most stable isohexide, followed by isosorbide and IM.…”

“…Synthesis of (3S,6S)-dimethyl hexahydrofuro [3,2-b]furan-3,6-dicarboxylate (IIDMC) monomer According to a reported procedure, isoidide dinitrile (IIDN) was synthetized from isomannide. 19 IIDN was further converted into (3S,6S)-dimethyl hexahydrofuro [3,2-b]furan-3,6-dicarboxylate (IIDMC). In a 100 mL one-necked round-bottom flask equipped with a magnetic stirrer and a reflux condenser, methanol (20-40 mL), HCl (32%, 20-40 mL), and IIDN (1,5-3 g) were sequentially charged.…”

“…Recently, a 1-carbon extended isohexide derivative with methyl ester functionality, namely isoidide dimethyl ester (IIDMC), has been reported as a comonomer for the synthesis of sugar-based polyesters with enhanced Tg. 19 So far, polymerizations involving this novel monomer were only performed using conventional metal-based catalysts.…”

Partially bio-based polyimides from isohexide-derived diamines

“…As a result, it is difficult to prepare high-molecular-weight polymers using isohexide as the sole monomers. 8,10 Therefore, many chemical modifications have been explored to enhance the reactivity of isohexides, including chain extensions by nucleophilic substitution, 10 as well as the introduction of more reactive functionalities, such as amines, [21][22][23] primary hydroxyl groups, [24][25] carboxylic acids, 25-26 and isocyanates. [27][28] Polymers with reasonably high molecular weights can be easily prepared using these isohexide derivatives.…”

Synthesis and characterization of novel biosourced building blocks from isosorbide

“…[3][4][5][6] More specifically, isosorbide (Is), the most produced monomer on industrial scale, was extensively investigated but suffered from a lack of reactivity on its hydroxyl functions [7] Therefore in order to be used in commercial polymers, more reactive 1,4:3,6-dianhydrohexitols derivatives were needed. In this field, several interesting works dealt with their transformation into amines, [8,9] acids, [10] or extended primary alcohols. [11] In this context, the majority of interest was focused on isosorbide as being central core and the modification was mainly considered at both extremities in order to build diesters [12,13] or oligoesters, diglycidyl ethers, [14] diamines, [15][16][17] diacids [18], and so on.…”