Catalytic Site‐, Diastereo‐, and Enantioselective Cascade Iodocyclization of 2‐Geranylarenols. Issue 7 (13th February 2023)

• Record Type: Journal Article
• Authors: Tsuji, Yasutaka; Kon, Kazumasa; Horibe, Takahiro; Ishihara, Kazuaki
• Is Part Of: Chemistry, an Asian journal. Volume 18:Issue 7(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-02-13
• Subjects: halogen bonding -- iodocyclization -- amidophosphate catalyst -- chiral Lewis base -- polyene cyclization; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.202300019
• Languages: English
• ISSNs: 1861-4728

Abstract

Abstract: A chiral amidophosphate‐ N ‐iodosuccinimide cooperative catalysis has been developed for the site‐, diastereo‐, and enantioselective iodocyclization of 2‐geranylarenols with molecular iodine to give the corresponding iodo‐containing polycyclic compounds with good levels of selectivity. This is the first example of a catalytic enantioselective iodocarbocyclization. A reactive chiral iodonium species is generated from molecular iodine via the dual halogen‐bonding interactions with a chiral Lewis base and Lewis acid. The sterically demanding 3, 3′‐substituents of the chiral BINOL‐derived amidophosphate are critical to induce the site‐selective iodination at the less‐hindered terminal alkenyl moiety of 2‐geranylarenols. Abstract : A nucleophilic chiral amidophosphate‐halo‐Lewis acid cooperative catalysis has been developed for the site‐, diastereo‐, and enantioselective iodocyclization of 2‐geranylarenols with molecular iodine to give the corresponding iodo‐containing polycyclic compounds with good levels of selectivity. The sterically demanding 3, 3′‐substituents of the chiral amidophosphate derived from ( R )‐BINOL are critical to induce the site‐selective iodination at the less‐hindered terminal alkenyl moiety of the 2‐geranylarenols.