SummaryCooperative activation using halogen bonding and hydrogen bonding works in metal-catalyzed asymmetric halolactonization. The Zn3(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 I2. Density functional theory calculations revealed that a catalytic amount of I2 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-I2 complex proceeds with the regeneration of I2, which enables the catalytic use of I2. The actual iodination reagent is I2 and not NIS.

Catalytic asymmetric iodoesterification of simple alkenes was achieved using a dinuclear zinc‐3,3′‐(R,S,S)‐bis(aminoimino)binaphthoxide (di‐Zn) complex. For iodoesterification using p‐methoxybenzoic acid, the N‐iodonaphthalenimide (NIN)‐I2 system was effective for producing iodoesters in a highly enantioselective manner. The synthetic utility of chiral iodo‐p‐methoxybenzoates was also demonstrated. The quartet of metal ionic bond, hydrogen bond, halogen bond, and π‐π stacking is harmonized on the single reaction sphere of di‐Zn catalyst for enabling the highly enantioselective catalytic asymmetric iodoesterification of simple alkenes for the first time.

Catalytic asymmetric iodoesterification of simple alkenes was achieved using a dinuclear zinc‐3,3′‐(R,S,S)‐bis(aminoimino)binaphthoxide (di‐Zn) complex. For iodoesterification using p‐methoxybenzoic acid, the N‐iodonaphthalenimide (NIN)‐I2 system was effective for producing iodoesters in a highly enantioselective manner. The synthetic utility of chiral iodo‐p‐methoxybenzoates was also demonstrated. The quartet of metal ionic bond, hydrogen bond, halogen bond, and π‐π stacking is harmonized on the single reaction sphere of di‐Zn catalyst for enabling the highly enantioselective catalytic asymmetric iodoesterification of simple alkenes for the first time.

Halogenveresterungen , die leicht erhältliche Alkene und Carbonsäuren umsetzen, haben eindeutige Vorteile für den industriellen Einsatz. Die erste allgemeine katalytische asymmetrische Iodveresterung von einfachen Alkenen wurde in der Zuchrift auf S. 12780 von T. Arai et al. durch Verwendung eines zweikernigen Zink‐3,3′‐(R,S,S)‐Bis(aminoimino)binaphthoxid‐Komplexes (di‐Zn) erreicht. Das Bild illustriert ein harmonisches Quartett aus ionischer Metallbindung, Wasserstoffbrücke, Halogenbrücke und π‐π‐Stapelung, die zusammen die asymmetrische Iodveresterung einfacher Alkene vermitteln.

Haloesterifications using easily obtainable alkenes and carboxylic acids have unique industrial benefits. The first general catalytic asymmetric iodoesterification of simple alkenes was achieved by T. Arai and co‐workers in their Communication on page 12680 by using a dinuclear zinc‐3,3′‐(R,S,S)‐bis(aminoimino)binaphthoxide complex. The picture represents a harmonizing quartet of metal ionic bond, hydrogen bond, halogen bond, and π–π stacking, acting together to enable the asymmetric iodoesterification of simple alkenes.