Aza-Peterson Olefinations: Rapid Synthesis of (E)-Alkenes

An aza-Peterson olefination methodology to access 1,3-dienes and stilbene derivatives from the corresponding allyl- or benzyl trimethylsilanes is described. Silanes can be deprotonated using Schlosser’s base and added into N-phenyl imines or ketones to directly give the desired products in high yields.

Tandem Peterson olefination and chemoselective asymmetric hydrogenation of β-hydroxy silanes

Tandem Peterson olefination and asymmetric hydrogenation of β-hydroxy silanes provides an efficient route to access the chiral benzylic hydrocarbon. The chemoselectivity can be tuned by the addition of base.

Synthesis of 8-Oxabicyclo[3.2.1]octanes by TiCl4-Mediated Reactions of 3-Alkoxycyclobutanones and Allenylsilanes

1-Substituted allenylsilanes reacted with 3-alkoxycyclobutanones in the presence of TiCl4 to afford 8-oxabicyclo[3.2.1]octan-3-ones stereoselectively. Nucleophilic attack of allenylsilanes to a 1,4-zwitterionic intermediate formed from 3-alkoxycyclobutanones and TiCl4­ followed by 1,2-silyl migration, five-membered cyclization with an alkoxy group, and seven-membered cyclization of titanium enolate was proposed. Deuteration and one-pot Peterson olefination suggested that alkyl titanium species were formed after cyclization to 8-oxabi­cyclo[3.2.1]octane skeletons.