Organocatalytic Asymmetric Mannich Addition of 3‑Fluorooxindoles to Dibenzo[<i>b</i>,<i>f</i>][1,4]oxazepines: Highly Enantioselective Construction of Tetrasubstituted C–F Stereocenters

3-Fluorooxindoles and the dibenzo­[b,f]­[1,4]­oxazepane scaffolds are important pharmacophores that have important application in medicinal chemistry. An organocatalyzed asymmetric Mannich reaction of 3-fluorooxindoles with dibenzo­[b,f]­[1,4]­oxazepines affording various seven-member cyclic amines containing chiral tetrasubstituted C–F stereocenters was developed. These reactions which were catalyzed by a bifunctional Cinchona alkaloid-derived thiourea catalyst afforded a wide range of substrates in moderate to high yields with excellent diastereo- and enantioselectivities (up to 88% yield, >20:1 dr and >99% ee). A feasible reaction mechanism was also proposed.