POS1-0360
Amide-Containing Methylene Malonamates for Photoredox Decarboxylative Construction of Sequence-Defined Vinyl Architectures
When and Where
Nov 30, -0001
12:00am - 12:00am
Presenter(s)
Kim Ju Eun (Seoul National University)
Co-Author(s)
Abstract
Conventional polymerization inherently produces molecular weight distributions and limited control over monomer sequence, making it difficult to prepare molecularly precise macromolecular architectures. Recent studies have shown that bulky vinyl building blocks can be sequentially incorporated through photoredox decarboxylation chemistry to generate sequence-controlled vinyl architectures. In these systems, adamantyl-substituted vinyl monomers suppress undesired side reactions through steric effects and contribute to controlled radical addition, enabling access to discrete vinyl structures with defined sequences.
In this work, we designed an amide-containing adamantyl methylene malonamate monomer as a functional alternative to previously reported adamantyl vinyl monomers. While retaining the adamantyl group for steric control, the vinyl building block was redesigned by replacing the ester linkage with an amide-containing methylene malonamate framework. Compared with ester-based analogues, amides provide distinct electronic properties and a versatile site for structural modification.
The synthesized monomer was investigated in photoredox reactions with amino acid-derived substrates, including Ac-alanine and Boc-proline derivatives. By introducing a methylene malonamate framework, this study expands the chemical space available for sequence-controlled vinyl structures beyond previously reported adamantyl-based monomers.
The amide functionality also enables systematic variation through modification of the amide substituent, allowing potential incorporation of diverse functional groups while maintaining compatibility with sequential radical addition chemistry. Ongoing studies focus on repeated incorporation of this monomer to construct longer discrete oligomers. Combining sequence control with tunable amide-derived functionality may provide access to peptide-inspired synthetic macromolecules and functionally programmed vinyl materials.
In this work, we designed an amide-containing adamantyl methylene malonamate monomer as a functional alternative to previously reported adamantyl vinyl monomers. While retaining the adamantyl group for steric control, the vinyl building block was redesigned by replacing the ester linkage with an amide-containing methylene malonamate framework. Compared with ester-based analogues, amides provide distinct electronic properties and a versatile site for structural modification.
The synthesized monomer was investigated in photoredox reactions with amino acid-derived substrates, including Ac-alanine and Boc-proline derivatives. By introducing a methylene malonamate framework, this study expands the chemical space available for sequence-controlled vinyl structures beyond previously reported adamantyl-based monomers.
The amide functionality also enables systematic variation through modification of the amide substituent, allowing potential incorporation of diverse functional groups while maintaining compatibility with sequential radical addition chemistry. Ongoing studies focus on repeated incorporation of this monomer to construct longer discrete oligomers. Combining sequence control with tunable amide-derived functionality may provide access to peptide-inspired synthetic macromolecules and functionally programmed vinyl materials.
