Catalytic Enantioselective Inverse Electron Demand Hetero‐Diels–Alder Reaction with Allylsilanes

Yuki Matsumura, Takahiro Suzuki, Akira Sakakura,* Kazuaki Ishihara * 
Angew. Chem. Int. Ed.201453 (24), 6131–6134.  (Published online: 29 Apr 2014) 
DOI: 10.1002/anie.201402934LinkIcon

New on the block:  The first diastereo‐ and enantioselective title reaction of β,γ‐unsaturated α‐ketoesters with allylsilanes is described. Chiral copper(II) catalysts successfully activate the β,γ‐unsaturated α‐ketoesters and promote the reaction with allylsilanes with excellent enantioselectivities. This process represents a new entry to chiral oxanes, which are useful building blocks. Tf=trifluoromethanesulfonyl.