Urea- and Thiourea-Substituted Cinchona Alkaloid Derivatives as Highly Efficient Bifunctional Organocatalysts for the Asymmetric Addition of Malonate to Nitroalkenes: Inversion of Configuration at C9 Dramatically Improves Catalyst Performance

Natural not always best: Novel N‐aryl urea and thiourea derivatives of dihydrocinchona alkaloids serve as efficient catalysts for the asymmetric addition of dimethyl malonate to a range of nitroalkenes. Catalytic activity and selectivity depend strongly on the relative configuration at C8/C9. Catalysts with “non‐natural” inverted configuration at C9 display excellent activity and enantioselectivity at loadings as low as 0.5 mol %.