Efficient Post-Polymerization modification of pendant aldehyde functional polymer via reductive etherification reaction

Polyether Synthesis through Reductive Etherification Reaction Strategy

“…As part of ongoing efforts on RER implementations, our group employed a polymer backbone with side‐chain aldehyde units ( M n = 80.1 kDa, D = 2.79) prepared using a conventional free radical polymerization, followed by modification with various alcohols in the presence of CDMS ( Scheme ). [ 74 ] A variety of alcohols (two equivalents per aldehyde) and CDMS (four equivalents per aldehyde) were efficiently reacted with pendant aldehyde functionalized polymer to give the corresponding ethers. As expected, the RER proceeded in quantitative or near‐quantitative yields for studied alcohols in this work.…”

“…The authors pointed out that primary or secondary alcohols, regardless of alcohol structure, proceeded via the RER mechanism and showed great tolerance to the alkene, alkyne, and halogen functionalities. [ 74 ] This strategy was also applied to thiol compounds. When thiols were used, a mole ratio of reactants (aldehyde and thiol) and CDMS was found to be 1:3:4, respectively.…”

A straightforward and rapid synthesis of polydithioacetals in the presence of chlorodimethylsilane

“…[51][52][53][54][55][56][57] After the pioneering studies of Doyle on the RER, this strategy has been successfully employed at the macromolecular level by successive studies of the Yokozawa group [58][59][60][61][62] and the recently published studies by our group. [63][64][65][66][67] Notably, our studies have shown that chlorodimethylsilane (CDMS), which has both reducing agent and Lewis acid characteristics, introduced by Lee and Morandi, 68 is an effective silane compound for obtaining polyethers as well as alkoxy pendant polymers. 63,64 More recently, we showed that when a polymer possessing pendant aldehyde units was subjected to a CDMSmediated RER using thiols, thioacetal and thioether structures were obtained in the side chain of the polymer.…”

“…63,64 More recently, we showed that when a polymer possessing pendant aldehyde units was subjected to a CDMSmediated RER using thiols, thioacetal and thioether structures were obtained in the side chain of the polymer. 65 Inspired by this study, we envisioned using CDMS for linear PDTA synthesis and innovating a new synthesis method for this polymer structure. Hence, this paper aims to provide an in-depth overview of CDMS-mediated PDTA synthesis.…”

Poly(silyl ether)s (silyl ether copolymers) via hydrosilylation of carbonyl compounds

“…In the RER protocol, carbonyl compounds in the presence of silane and a Brønsted or Lewis acid catalyst afford the synthesis of symmetric and unsymmetrical ethers. 8–28 However, the silyl ether is produced rather than the corresponding ether in the hydrosilylation. Notably, both mechanisms seem to cover the competing reaction pathways.…”