Polyether Synthesis through Reductive Etherification Reaction Strategy

Abstract

The reductive etherification reaction (RER) of carbonyl groups (aldehydes or ketones) through silane as a reducing agent together with Bronsted or Lewis acid affords the synthesis of symmetrical and unsymmetrical ethers. This strategy is applied at the macromolecular level for the first time in 1993, and isophthalaldehyde is self‐polymerized in the presence of triethylsilane (Et3SiH)/ tritylperchlorate (TrClO4) to yield polyethers with low to moderate molecular weights. Next, the polyethers with alternating structures are achieved by reacting isophthalaldehyde with bis(trimethylsilyl) ethers or diols as comonomers using reducing agent silane and Lewis acid. Moreover, in recent years, it is shown that polyether synthesis and post‐polymerization modification (PPM) of polymers proceeds smoothly and effectively with the RER strategy in the presence of chlorodimethylsilane (CDMS), which acts as both a reducing agent and a Lewis acid.

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.…”