Single-Handed Helical Poly(quinoxaline-2,3-diyl)s Bearing Achiral 4-Aminopyrid-3-yl Pendants as Highly Enantioselective, Reusable Chiral Nucleophilic Organocatalysts in the Steglich Reaction

Takeshi Yamamoto; Ryo Murakami; Michinori Suginome

doi:10.1021/jacs.6b12349

Single-Handed Helical Poly(quinoxaline-2,3-diyl)s Bearing Achiral 4-Aminopyrid-3-yl Pendants as Highly Enantioselective, Reusable Chiral Nucleophilic Organocatalysts in the Steglich Reaction

J Am Chem Soc. 2017 Feb 22;139(7):2557-2560. doi: 10.1021/jacs.6b12349. Epub 2017 Feb 10.

Authors

Takeshi Yamamoto¹, Ryo Murakami¹, Michinori Suginome¹

Affiliation

¹ Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University , Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.

PMID: 28161948
DOI: 10.1021/jacs.6b12349

Abstract

Helically chiral poly(quinoxaline-2,3-diyl)s bearing 4-aminopyrid-3-yl pendants were synthesized as new helical-polymer-based chiral nucleophilic organocatalysts. The obtained chiral nucleophilic polymer catalysts exhibited high catalytic activity, enantioselectivity, and reusability in asymmetric Steglich rearrangement of oxazolyl carbonate to C-carboxyazlactone. The polyquinoxaline-based, helically chiral DMAP catalyst mediated intramolecular acyl transfer selectively, by contrast with known small-molecule-based chiral organocatalysts, which also mediate intermolecular acyl transfers.

Publication types

Research Support, Non-U.S. Gov't