744 Letters in Organic Chemistry, 2006, 3, 744-748 1,2-Glycerol Carbonate: A Versatile Renewable Synthon Ana-Catarina Simão a,b , Benita Lynikaite-Pukleviciene a,c , Cyril Rousseau c , Arnaud Tatibouët *,a , Stéphanie Cassel a , Algirdas Sackus c , ˘ ˘ Amelia P. Rauter b and Patrick Rollin *,a a I.C.O.A. - UMR 6005,Université d'Orléans, BP 6759, F-45067 Orléans, France b F.C.U.L. - Campo Grande, Edifício C5, Lisboa, Portugal c K.T.U. - Chemines . Technologijos Fakultetas, LT-50270 Kaunas, Lithuania Received July 04, 2006: Revised October 03, 2006: Accepted October 03, 2006 Abstract: Activated 1,2-glycerol carbonate has been subjected to nucleophilic substitution with oxygen-, nitrogen- and sulfur nucleophiles. Selective reactions with thiol derivatives have been especially investigated for the preparation of mono- and dithiofunctionalized 3-carbon synthons. Keywords: Glycerol carbonate, renewable resources, thiofunctionalization, oxidation. INTRODUCTION been investigated using lipase-catalysed acetylation and/or alcoholysis [5a]. More recently, self-condensation to oligomers has been explored [6], but little has been developed on chemical transformations of 2 when treated with various nucleophiles. Our interest is focused on the versatility of such an activated form of glycerol as a multi- electrophilic synthon in which the primary hydroxyl group can also be activated (Scheme 2). Glycerol carbonate might Valorisation of glycerol 1 is becoming a crucial challenge for industrial companies: this small molecule appears as a major side-product during manufacturing of bio-diesels, fatty acids and surfactants [1]. This abundant and renewable itol is a prochiral C-3 synthon which has been widely investigated and used as raw material [2]. Among the glycerol-based O O O HO OH OH HO O O HO O O HO X O O O 4 2 1 3 Nu 4 elec tes t rophil ic si Scheme 1. Classical synthons from glycerol and proposed site reactivities of activated 1,2-glycerol carbonate. cyclic acetals (Scheme 1), 1,2-O-derivatives have been largely described and studied mainly as a source of chirality [3]. In contrast to its ready accessibility [4], 1,2-glycerol carbonate 2 has been scarcely studied as precursor for the development of new synthons in organic chemistry [5]. thus be regarded as an alternative synthon to glycidol or activated glycidols, with a highly reduced toxicity [7]. RESULTS AND DISCUSSION Activation of the free alcohol function of 2 through sulfonate formation using mesyl or tosyl chloride under basic conditions gave 5 or 6 in 92% and 99% yield respectively. No side-product was detected in the tosylation process while predictable chloride ion counter-attack occurred during mesylation, albeit in 6% yield only. Mesylate 5 was used first to test the displacement with a few standard nucleophiles (Table 1). Compared to Solketal® (1,2-O-isopropylideneglycerol) 3, the reactivity potential of glycerol carbonate 2 is by far more important. The resolution of racemic 2 has already *Address correspondence to these authors at the I.C.O.A. – UMR 6005, Université d'Orléans, BP 6759, F-45067 Orléans, France; Tel: 33(0)238417370; Fax: 33(0)238417281; The preliminary results showed rather poor yields for a selective nucleophilic mono-substitution (products 7-11a). E-mail: patrick.rollin@univ-orleans.fr; arnaud.tatibouet@univ-orleans.fr 1570-1786/06 $50.00+.00 © 2006 Bentham Science Publishers Ltd.