Association of Halogen Bonding and Hydrogen Bonding in Metal Acetate-Catalyzed Asymmetric Halolactonization

Cooperative activation using halogen bonding and hydrogen bonding works in metal-catalyzed asymmetric halolactonization. The Zn(3)(OAc)(4)-3,3′-bis(aminoimino)binaphthoxide (tri-Zn) complex catalyzes both asymmetric iodolactonization and bromolactonization. Carboxylic acid substrates are converted to zinc carboxylates on the tri-Zn complex, and the N-halosuccinimide (N-bromosuccinimide [NBS] or N-iodosuccinimide [NIS]) is activated by hydrogen bonding with the diamine unit of chiral ligand. Halolactonization is significantly enhanced by the addition of catalytic I(2). Density functional theory calculations revealed that a catalytic amount of I(2) mediates the alkene portion of the substrates and NIS to realize highly enantioselective iodolactonization. The tri-Zn catalyst activates both sides of the carboxylic acid and alkene moiety, so that asymmetric five-membered iodolactonization of prochiral diallyl acetic acids proceeded to afford the chiral γ-butyrolactones. In the total description of the catalytic cycle, iodolactonization using the NIS-I(2) complex proceeds with the regeneration of I(2), which enables the catalytic use of I(2). The actual iodination reagent is I(2) and not NIS.