Synthesis and characterization of functional six-membered ring carbonates for the preparation of orthogonal couplers

Abstract

On the basis of commercially available trimethylolpropane (TMP) three six-membered ring carbonates were prepared, substituted with reactive side groups: a chloroformate (2a), an imidazolyl carbamate (2b) and a phenyl carbonate (2c). Their synthesis and characterizations are described and compared to known ring carbonates with reactive side groups. Starting from 2a-c orthogonal couplers 3a and 3b were synthesized for conversion under mild reaction conditions. In a model reaction 2-azidoethyl 2-N-acetylamino-2-deoxy--D-glucopyranose and tertbutyl-N-(3-aminopropyl) carbamate were linked with coupler 3a via a 1,3-dipolar cycloaddition and a nucleophilic ring-opening reaction. This coupling principle can be used for the preparation of multifunctional polymers or surface coatings at ambient conditions.

Synthesis of a Difunctional Orthogonal Coupler for the Preparation of Carbohydrate‐Functionalized sP(EO‐stat‐PO) Hydrogels

“…The 1 H NMR spectrum of 4 shows signals typical of a six-membered cyclic carbonate at d ¼ 4.32 and 4.17 (H 5 ). [7,37] After the ring-opening reaction, these signals disappear and new signals at d ¼ 4.04 (H 6 ) and d ¼ 3.43 (H 4 ), consistent with the formation of the functionalized coupler 5 appear. In the 13 C NMR spectrum of coupler 4, signals typical of a sixmembered cyclic carbonate were observed at d ¼ 148.5 (C 9 ) and 72.7 (C 5 ).…”

“…Cyclization of diol 3 to the difunctional orthogonal coupler 4 was performed with ethyl chloroformate and TEA as described. [7,35] Coupler 4 consists of a sixmembered ring carbonate with a propargyl ether side group, and is similar to a previously described orthogonal coupler. [7] The difference between these couplers is the functional group used for linking the propargyl group to the sixmembered ring carbonate: an ether group in coupler 4 versus a urethane group.…”

“…accomplish this, an orthogonal difunctional coupler, a sixmembered ring carbonate with a propargyl ether side chain, which is based on trimethylolpropane (TMP), was synthesized, and is able to connect building blocks via orthogonal reactions. [7] Our aim was to prepare carbohydrate and glycan building blocks for glycoarrays and glycopolymers, which are becoming increasingly important in glycobiology and glycobiotechnology.…”

Poly(amide urethane)s with functional/reactive side groups based on a bis-cyclic bio-based monomer/coupling agent

“…Using two different amines and one of the AA 0 dicarbonate monomers alternating copolymers can be obtained, if the two amines are added consecutively: first 0.5 equivalent of NH 2 -R 1 -NH 2 and after full conversion another 0.5 equivalent of NH 2 -R 2 -NH 2 [19][20][21][22][23][24][25][26]. The resulting hydroxyl functional polyurethanes are amorphous materials; the glass transition temperature can be adjusted in a large range; of special interest being those with 20 < T G < 50°C.…”

Hydroxyl‐functional polyurethanes and polyesters: synthesis, properties and potential biomedical application

“…Carbonate monomers for this procedure are either prepared from triols which are converted first to hydroxyl‐functional cyclic carbonates and then connected together to result in AA‐type monomers with two identical cyclic carbonate end groups, or these hydroxyl‐functional cyclic carbonates are reacted with phenyl chloroformate to result in AA′‐type monomers with a cyclic carbonate and a phenylcarbonate group. Both monomers, the AA‐type and the AA′‐type, result in hydroxyl‐functional polyurethanes upon reaction with diamines 7–10. (iii) In a third approach multifunctional polyurethanes are prepared from carbonate couplers, functional amines and polyamines.…”