New Functionalized Anionic Initiators Prepared from Substituted 1,1‐Diphenylethylene Derivatives with Acetal‐Protected Monosaccharides and Their Application to Chain‐Multi‐Functionalized Polymers with Glucose and Galactose Molecules

Abstract

Living anionic polymerizations of methyl methacrylate, tert‐butyl methacrylate, 2‐(perfluorobutyl)ethyl methacrylate, tert‐butyl acrylate, and ethylene oxide were carried out with functionalized initiators prepared from substituted 1,1‐diphenylethylene (DPE) derivatives with two and four acetal‐protected α‐D‐glucofuranose and α‐D‐galactopyranose residues and carbanionic species such as sec‐butyllithium (sec‐BuLi), cumylpotassium, lithium and potassium naphthalenides. In certain cases, either LiCl or diethylzinc was used as an additive to control the polymerization. Several new well‐defined chain‐end‐ and in‐chain‐functionalized polymers with two and four glucose and two galactose molecules were successfully synthesized by these living polymerizations followed by deprotection. We have proposed a promising iterative methodology based on a convergent approach, with which novel two dendritic substituted DPE derivatives with four and eight acetal‐protected D‐glucofuranose residues can successively be synthesized. With use of the functionalized anionic initiators prepared from such dendritic DPE derivatives and sec‐BuLi in the polymerization of methyl methacrylate, well‐defined chain‐end‐functionalized poly(methyl methacrylate)s with four and eight glucose molecules were synthesized.magnified image

Precise synthesis of well‐defined dendrimer‐like star‐branched polymers by iterative methodology based on living anionic polymerization

“…Similarly, it was possible to readily synthesize a DPE derivative with eight SMP groups, 4 , by repeating the same reaction sequence starting from 3 . Thus, the iterative methodology using the aforementioned reaction sequence can gain easy access to DPE derivatives with four, eight, and possibly more SMP groups 50, 51…”

Synthesis of asymmetric star‐branched polymers consisting of three or four different segments in composition by means of living anionic polymerization with a new dual‐functionalized 1,1‐bis(3‐chloromethylphenyl)ethylene

“…Under an atmosphere of nitrogen, NaH (2.46 g, 102 mmol) was slowly added at 0 °C to a stirred solution of 4‐hydroxystyrene (10.2 g, 84.9 mmol) and 4‐[4‐(1,2:5,6‐di‐ O ‐isopropylidene‐α‐ D ‐glucofuranose‐3‐oxy)butyl bromide (33.5 g, 85.0 mmol), the synthetic procedure for which has been described elsewhere,41 dissolved in 200 mL of dry dimethylformamide (DMF). Then, the mixture was stirred for 24 h at room temperature.…”