Zirconium enolates,
derived from copper-catalyzed asymmetric conjugate
additions, are trapped with the Vilsmeier–Haack reagent. Asymmetric
additions generate quaternary carbon centers with high enantioselectivity
(generally ∼90% ee), and the enolates are converted to unsaturated
β-chloroaldehydes (41–57% yields). The reaction tolerates
changes to the nucleophile, can be used to form five-, six-, or seven-membered
ring products, and is scalable to 5 mmol, and the products are readily
elaborated by condensation, cross coupling, and addition reactions.