Vinyl-Addition Polymerizations of Borylated Allenes

Abstract

Borylated motifs hold immense potential for functional soft materials, as they can facilitate a range of reaction manifolds (e.g., analyte binding or cross-coupling). Traditional boron-containing materials are predominantly composed of either aryl boronates or main-chain embedded vinylic boronates. Progress toward expanding the architectural (and, by extension, functional) scope of borylated polymers remains slightly limited. To address this, we report the vinyl-addition polymerization of an allenylboronic acid pinacol ester. The base metal catalyst, [(η3-C 3 H 5 )Ni-(OC(O)CF 3 )] 2 , was found to readily polymerize this allene monomer with good regioselectivity and molecular weight control. Additionally, the allenylboronate monomer could be copolymerized with other allenes (e.g., 1,2-nonadiene or β-pinadiene) to access an array of borylated materials. The borylated polyallenes could also be chemically tailored under mild conditions (e.g., using Pdcatalyzed cross-coupling), which suggests that they could serve as general platforms for accessing diverse architectures.

Ring Opening Copolymerization of Boron-Containing Anhydride with Epoxides as a Controlled Platform to Functional Polyesters

“…These vinyl monomers are polymerized either by free or controlled radical polymerizations, including reversible addition–fragmentation chain-transfer, RAFT, , and atom-transfer radical polymerization, ATRP . Recently, more sophisticated structures have been obtained by olefin addition polymerization of allenyl- or vinylboronate esters − or by ring-opening metathesis polymerization of 1,1-bis­(boryl)­cyclohexene . Critically, all these routes furnish hydrocarbon polymer backbones which may complicate any future recycling and usually prevent degradation.…”

Reversibly photoswitchable catalysts for high regioselectivity and enantioselectivity in polymerization of allenes

“…[4][5][6] There is still a great desire to develop a novel strategy for high regioselectivity and living/controlled polymerization of allene monomers. [7][8][9] On the other hand, optically active helical polyallenes were generally obtained through polymerization of chiral allene monomers. The chirality of the monomers determined the helical sense of the main chain in polyallenes, so a large number of chiral monomers were obtainable in the process of the polymerization.…”

Vinyl boronate polymers with dynamic exchange properties

“…21 Lately, we have demonstrated the synthesis of phenyl N-methyliminodiacetic acid (MIDA) boronate-containing monomers and achieved their atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization. 22,23 In addition, alkenyl boronate monomers were also applied to radical [24][25][26] or metalcatalyzed polymerization, 27,28 enriching the methods of preparing boron-containing polymers.…”