Total Synthesis of GKK1032A2 via Direct 13-Membered Macrocyclization Using a Nucleophilic Aromatic Substitution of an (η6 -Arene)Chromium Complex.

The first enantioselective total synthesis of GKK1032A2 has been achieved. The key step is a direct construction of the highly strained 13-membered macrocycle of GKK1032A2 by an intramolecular nucleophilic aromatic substitution (SN Ar) reaction. This is the first successful example of construction of a macrocycle with an aryl ether linkage utilizing an intramolecular SN Ar reaction of an (η6 -arene)chromium complex.