Synthesis of Chiral Poly(silyl ether)s via CuH-Catalyzed Asymmetric Hydrosilylation Polymerization of Diketones with Silanes.

The precise synthesis of chiral poly(silyl ether)s remains a challenge, in contrast to the well-studied preparation of poly(silyl ether)s. Herein, an unprecedented approach for the synthesis of optically active poly(silyl ether)s with main-chain chirality has been developed via CuH-catalyzed hydrosilylation polymerization of diketones and silanes. The polymerization features low catalyst loading, mild condition, and broad substrate scope, including a wide range of aromatic diketones and heteroaromatic diketones with excellent yields and enantioselectivities (up to 98% yield and 99% ee). Thermal analysis indicated chiral poly(silyl ether)s exhibit good thermal properties. These enantiomerically enriched poly(silyl ether)s with good thermal stability have a promising application in chiral separation.