The β-azido functionalization reaction provides a mechanistically different enone synthesis that involves treatment of 2 with fluoride anion to effect desilylation and concomitant β-elimination to give 3. Table 1 lists a number of examples of the direct conversion of a TIPS enol ether into the corresponding R,β-enone via a β-azido TIPS enol ether. The β-azido group can be ionized with Me 3 Al or Me 2 AlCl and the intermediate enonium ion trapped by a variety of nucleophiles such as an allylstannane, electron-rich aromatics, TMS enol ethers, Et 2 AlCN, Me 2 AlCCR, Me 4 AlLi, and vinylaluminum reagents to give the products listed in Table 2. The diastereoselectivity of the reaction of a 4-substituted enonium ion with indole shows an unusual increase of selectivity with increasing temperature. Reduction of the azide 2 provides access to β-amino TIPS enol ethers 5, which, for example, can be converted into a cinnamide derivative and cyclized via a putative "ene" process into a γ-lactam.