Silyl Ketene Imines

Enantioselective construction of quaternary stereogenic carbons by the Lewis base catalyzed additions of silyl ketene imines to aldehydes.

Silyl ketene imines derived from a variety of alpha-branched nitriles have been developed as highly useful reagents for the construction of quaternary stereogenic centers via the aldol addition reaction. In the presence of SiCl4 and the catalytic action of chiral phosphoramide (R,R)-5, silyl ketene imines undergo extremely rapid and high yielding addition to a wide variety of aromatic aldehydes...

Gallium tribromide catalyzed coupling reaction of alkenyl ethers with ketene silyl acetals.

Enantioselective acylation of silyl ketene acetals through fluoride anion-binding catalysis.

A highly enantioselective acylation of silyl ketene acetals with acyl fluorides has been developed to generate useful α,α-disubstituted butyrolactone products. This transformation is promoted by a new thiourea catalyst and 4-pyrrolidinopyridine and represents the first example of enantioselective thiourea anion-binding catalysis with fluoride.

Carbogallation of alkynes using gallium tribromide and silyl ketene acetals and synthetic application to cross-coupling with aryl iodides.

Silyl Ketene Acetals/B(C6F5)3 Lewis Pair-Catalyzed Living Group Transfer Polymerization of Renewable Cyclic Acrylic Monomers

This work reveals the silyl ketene acetal (SKA)/B(C6F5)3 Lewis pair-catalyzed room-temperature group transfer polymerization (GTP) of polar acrylic monomers, including methyl linear methacrylate (MMA), and the biorenewable cyclic monomers γ-methyl-α-methylene-γ-butyrolactone (MMBL) and α-methylene-γ-butyrolactone (MBL) as well. The in situ NMR monitored reaction of SKA with B(C6F5)3 indicated t...