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Coordinative Chain Transfer Polymerization of Butadiene with Functionalized Aluminum Reagents.

ABSTRACT: Functionalized aluminum alkyls enable effective coordinative chain transfer polymerization with selective chain initiation by the functionalized alkyl. (ω-Aminoalkyl)diisobutylaluminum reagents (12 examples studied) obtained by hydroalumination of α-amino-ω-enes with diisobutylaluminum hydride promote the stereoselective catalytic chain growth of butadiene on aluminum in the presence of Nd(versatate)₃ , Cp*₂ Nd(allyl), or Cp*₂ Gd(allyl) precatalysts and [PhNMe₂ H⁺ ]/[B(C₆ F₅ )₄ ^- ]. Carbazolyl- and indolylaluminum reagents result in efficient molecular weight control and chain initiation by the aminoalkyl rather than the isobutyl substituent bound to aluminum. As confirmed for (3-(9H-carbazol-9-yl)propyl)-initiated polybutadiene (PBD), for example, by deuterium quenching studies, polymer chain transfer by β-hydride transfer is negligible in comparison to back-transfer to aluminum.

SUBMITTER: Gottker-Schnetmann I

PROVIDER: S-EPMC6899983 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The DNA-templated polymerization of synthetic building blocks provides a potential route to the laboratory evolution of sequence-defined polymers with structures and properties not necessarily limited to those of natural biopolymers. We previously reported the efficient and sequence-specific DNA-templated polymerization of peptide nucleic acid (PNA) aldehydes. Here, we report the enzyme-free, DNA-templated polymerization of side-chain-functionalized PNA tetramer and pentamer aldehydes. We observed that polymerization of tetramer and pentamer PNA building blocks with a single lysine-based side chain at various positions in the building block could proceed efficiently and sequence specifically. In addition, DNA-templated polymerization also proceeded efficiently and in a sequence-specific manner with pentamer PNA aldehydes containing two or three lysine side chains in a single building block to generate more densely functionalized polymers. To further our understanding of side-chain compatibility and expand the capabilities of this system, we also examined the polymerization efficiencies of 20 pentamer building blocks each containing one of five different side-chain groups and four different side-chain regio- and stereochemistries. Polymerization reactions were efficient for all five different side-chain groups and for three of the four combinations of side-chain regio- and stereochemistries. Differences in the efficiency and initial rate of polymerization correlate with the apparent melting temperature of each building block, which is dependent on side-chain regio- and stereochemistry but relatively insensitive to side-chain structure among the substrates tested. Our findings represent a significant step toward the evolution of sequence-defined synthetic polymers and also demonstrate that enzyme-free nucleic acid-templated polymerization can occur efficiently using substrates with a wide range of side-chain structures, functionalization positions within each building block, and functionalization densities.

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Coordinative Chain Transfer Polymerization of Butadiene with Functionalized Aluminum Reagents.

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