Azasilacyclopentanes

93–98% Yield

Silicon-nitrogen heterocycles synthesized by rare-earth-catalyzed selective hydrosilylation of iminocyclopropanes with primary silanes.

Yaxin, Feng · Fen, Wang · Xu, Xiufang · Zhu, Shoufei · Li, Jianfeng · Cui, Chunming

Journal of the American Chemical Society 2025

Specifications

Catalyst loading

{'zh': '0.5', 'en': '0.5'} mol%

Advantages

Mild and scalable

The reaction proceeds at room temperature with only 0.5 mol% catalyst loading and can be scaled up to gram scale, requiring no special equipment or harsh conditions.

Versatile product transformation

The azasilacyclopentanes readily undergo alcoholysis or hydrolysis to give amine-functionalized siloxanes and silanols, which are valuable intermediates in pharmaceutical and materials synthesis.

Mechanistic insight

Deuterium labeling, kinetic isotope effect experiments, and DFT calculations disclosed a cascade inter- and intramolecular hydrosilylation mechanism, and the key rare-earth hydride intermediate was isolated and characterized, guiding catalyst design.

Applications

• Silicon-containing drug intermediates：Provide silicon-containing heterocyclic building blocks for late-stage functionalization of drug-like scaffolds.
• Functionalized polysiloxanes：Hydrolysis yields silanols that serve as monomers for functionalized polysiloxanes.
• Chiral ligands：Expand the ligand library for rare-earth chiral catalysts in asymmetric catalysis.
• Organosilicon materials：Alcoholysis leads to amine-functionalized siloxanes for organosilicon material modification.