Highly Enantioselective Michael Addition of Silyl Nitronates to α,β-Unsaturated Aldehydes Catalyzed by Designer Chiral Ammonium Bifluorides:  Efficient Access to Optically Active γ-Nitro Aldehydes and Their Enol Silyl Ethers

Highly enantioselective Michael addition of silyl nitronates to α,β-unsaturated aldehydes has been accomplished by the utilization of designer N-spiro C2-symmetric chiral quaternary ammonium bifluoride 1 as an efficient catalyst, providing direct access to both optically active γ-nitro aldehydes, a very useful precursor to various complex organic molecules including aminocarbonyls, and their enol silyl ethers, a Mukaiyama donor of potential synthetic utility for further selective transformations. For instance, the reaction of trimethylsilyl nitronate 2 (R1 = Me) with trans-cinnamaldehyde (R2 = Ph, R3 = H) in toluene in the presence of (R,R)-1 (2 mol %) proceeded smoothly at −78 °C to give the desired enol silyl ether 3 (R1 = Me, R2 = Ph, R3 = H) in 90% isolated yield (anti/syn = 83:17) with 97% ee (anti isomer), and simple treatment of 3 thus obtained with 1 N HCl in THF at 0 °C afforded the corresponding γ-nitro aldehyde 4 quantitatively without loss of diastereo- and enantioselectivity.