Phosphoramitoids-A submonomer approach to sequence defined N-substituted phosphoramidate polymers

Area of Science:

• Polymer Chemistry
• Organic Synthesis
• Materials Science

Background:

• Growing demand for bio-inspired, chemically diverse, sequence-defined synthetic polymers.
• Solid-phase submonomer synthesis offers facile access to complex materials.
• Previous submonomer approaches focused on oligo-amide backbones.

Purpose of the Study:

• To extend solid-phase submonomer synthesis to phosphorous-containing backbones.
• To develop a method for constructing N-substituted phosphoramidate oligomers.
• To create sequence-defined polymers with diverse side chain functionalities.

Main Methods:

• Utilized a three-step solid-phase submonomer approach.
• Employed H-phosphonate (P III) chemistry for chain extension.
• Incorporated the Atherton-Todd reaction for side chain attachment.

Main Results:

• Successfully synthesized phosphoramidate oligomers with phosphorous-containing backbones.
• Achieved synthesis using cheap, stable reagents under mild conditions (air, no heating, <30 min reactions).
• Produced phosphoramitoid tetramers and pentamers with diverse side chains, typically >85% crude purity.

Conclusions:

• The developed method provides efficient access to novel phosphorous-containing synthetic polymers.
• The approach is versatile, allowing for diverse side chain functionalities.
• This work expands the scope of solid-phase submonomer synthesis for creating advanced materials.