Catalytic Asymmetric Iodoesterification of Simple Alkenes

Takayoshi Arai; Kodai Horigane; Takumi K Suzuki; Ryosuke Itoh; Masahiro Yamanaka

doi:10.1002/anie.202003886

Catalytic Asymmetric Iodoesterification of Simple Alkenes

Angew Chem Int Ed Engl. 2020 Jul 27;59(31):12680-12683. doi: 10.1002/anie.202003886. Epub 2020 May 26.

Authors

Takayoshi Arai¹, Kodai Horigane¹, Takumi K Suzuki¹, Ryosuke Itoh², Masahiro Yamanaka²

Affiliations

¹ Soft Molecular Activation Research Center (SMARC), Chiba Iodine Research Innovation Center (CIRIC), Molecular Chirality Research Center (MCRC), Department of Chemistry, Graduate School of Science, Chiba University, 1-33 Yayoi, Inage, Chiba, 263-8522, Japan.
² Department of Chemistry, Research Center for Smart Molecules, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo, 171-8588, Japan.

PMID: 32342634
DOI: 10.1002/anie.202003886

Abstract

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.

Keywords: asymmetry; catalysts; haloesterification; halogen bonding; π-π stacking.