Epoxy functionalized polymethacrylates based on various multifunctional d‐glucopyranoside acetals

Abstract

The synthesis of acetal‐derived d‐glucopyranosides with a various number of hydroxyl groups (the first step, acetalization) and their modified forms with bromoester groups (the second step, esterification) are presented here. The latter, due to the type of functional groups, can be used to initiate the controlled atom transfer radical polymerization. The copolymerizations of equimolar feed of methacrylate monomers, namely, methyl methacrylate and glycidyl methacrylate, were initiated by prepared new glycoinitiators, based on methyl α‐d‐glucopyranoside (MeαdGlu) or 2‐(hydroxymethyl)phenyl‐β‐d‐glucopyranoside (salicin), in the presence of the catalyst system CuCl/dNbpy in anisole at 30 °C. The conditions were sufficient for successful synthesis of well‐defined copolymers with sugar cores sheltered by two‐, three‐, four‐, or six‐polymethacrylate segments with various polymerization degrees (DParm = 15 – 70) and low dispersity indices (Ð = 1.15–1.30). Because of the presence of oxirane groups, the star‐copolymers can be functionalized in further steps by biologically active compounds or modified to amphipilics. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2483–2494

Lipase‐Catalyzed Synthesis of Substituted Phenylacetamides: Hammett Analysis and Computational Study of the Enzymatic Aminolysis

“…It has previously been reported that this protection reaction has been achieved through one‐step processes 7–28. However, these transformations require high temperature,7 extended reaction times,8–15 metal catalysts16–27 or stoichiometric catalysis 28. Recently, the organocatalytic synthesis of 4,6‐benzylidene glycosides from aromatic aldehydes in one step under mild conditions was reported by Schmidt and co‐workers 29.…”

Synthesis and characterization of D‐(−)‐Salicine‐based star copolymers containing pendant carboxyl groups with fluorophore dyes

“…The levorotary derivatives of d ‐(−)‐salicin (2‐(hydroxymethyl)phenyl‐β‐D‐glucopyranoside) ( I and II ) were prepared in two steps . The condensation of salicin with SLA or TPhA yielded the products with OCHO group(s) at C‐4 and C‐6 (C‐4′and C‐6′) corresponding to unsymetrical monoacetal, and symmetrical diacetal, respectively.…”

Synthesis and self-assembly behavior of amphiphilic methyl α-D-glucopyranoside-centered copolymers

“…Synthesis of methyl α-D-glucopyranoside-based initiators (GI1, GI2, GI3) ATRP sugar initiators based on methyl α-D-glucopyranoside were prepared according to previously described procedures [26]. The condensation of MeαDGlu and BZA (1:2) or SLA (1:4) or TPhA (2:1) in a benzene/DMF containing catalyst pTSA (0.2 g for GI1; 0.4 g for GI2 and GI3) was performed in argon with stirring, and then water was removed by a DeanStark apparatus, whereas the catalyst was deactivated with CaCO 3 , and filtered off.…”

“…The initiators (GI1-GI3) based on the acetal derivatives of methyl α-D-glucopyranoside with 2-bromoisobutyryl groups (f Br =2-4, Scheme 1), which are optically active and therefore indicating positive values of the specific rotation ([α] D =+32°− +44°), were applied [26]. They were prepared in a two-step procedure, that is i) the condensation of methyl α-Dglucopyranoside with benzaldehyde, salicylaldehyde, and terephthalaldehyde catalyzed by p-toluenesulfonic acid, and ii) the esterification of secondary hydroxyl groups by 2-bromoisobutyryl bromide.…”

“…Carbohydrate functionalized polymers are in great demand for biomedical applications, especially in pharmaceutical areas, molecular recognition processes, and as biomimetics or surfactants [25]. The multifunctionality of D-glucopyranoside derivatives used for the initiation of polymerization allowed us to obtain the well-defined topologies with predetermined numbers of segments/arms using the core-first strategy, which was previously studied in test polymerizations of the equimolar ratio of methacrylate comonomers [26]. This work was developed by using various ratios of comonomers, glycidyl methacrylate (GMA), and methyl methacrylate (MMA), which made it possible to predict the number of oxirane moieties in the copolymers (25-100 mol%) in relation to polymerization degrees.…”