Biomass represents an attractive renewable resource for an alternative production of chemicals and high value-added molecules. In the continuity of on-going projects orientated on green and sustainable chemistry, chemical transformation of biosourced molecules represents a synthetic challenge that is still on demand. Isosorbide, a chiral dianhydrohexitol, is a major product of the starch industry produced by Roquette Frères (Lestrem, France) who expanded its production to several thousands of tons in 2015. This renewable platform molecule is produced from D-sorbitol, following a double dehydration process. This availability allowed the promotion of isosorbide applications in various fields: polymers (polyethylene isosorbide terephthalate), surfactants, solvents (dimethyl isosorbide) and pharmacy (isosorbide dinitrate). Isosorbide properties opened the investigations as a chiral inducer either as a ligand, an auxiliary or a phase transfer catalyst. Other isohexides (isomannide, isoidide) were much less studied.<br/>These diastereomeric conformationally rigid structures offer a large diversity of modifications to tune their electronic / steric properties. Isohexides are promising candidates for the development of biosourced inexpensive metal-free catalysts. Very recently, Friedel-Crafts enantioselective alkylation of indole mediated by thiourea organocatalysts derived from isohexides has been described.<br/>In this communication, the functionalization of isohexides into aminoalcohols, aminoethers and diamines will be reported, as well as the preliminary results of their screening as potential organocatalysts in the synthesis of Warfarin.<br/>A second part of our project consisted in the synthesis of 1,2-diamines derivatives, known for their activity as catalysts in 1,4-addition reactions. Thus we considered the amide coupling between amino acids and amine derivatives of isosorbide, followed by reduction. As far as we know, amide bond formation on isohexide derivatives was always carried out with classical methods using an excess of reactant and stoichiometric amount of reagents (EDC, HOBt). We developed a promising simple method using catalytic amounts of boric acid and affording the desired amides by simple basic treatment with 60 to 90% yields.

Bio-based amines and amides from renewable isosorbide

253rd National Meeting (2017)

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