Thorpe-Ingold effect on the ATRP-induced cyclopolymerization of bismethacrylate tethered by a substituted silylene moiety
Journal
Macromolecular Chemistry and Physics
Journal Volume
213
Journal Issue
5
Pages
566-571
Date Issued
2012
Author(s)
Abstract
ATRP-induced cyclopolymerization of dialkylsilylene-tethered bismethacrylates leads to the corresponding polymethacrylate having fourteen-membered cyclic pendants. The presence of bulky substituents on silicon is essential to facilitate the overall cyclopolymerization process in 3. Simple methacrylate derivatives do not undergo polymerization under these conditions. This observation can be understood within the framework of the Thorpe-Ingold effect in organosilicon chemistry. The high rr stereoselectivity suggests that the cyclization step may selectively lead to the r diastereomer. Density functional theory calculations also show that r selectivity might be slightly favored. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Type
journal article