Synthesis of Ngai Reagent and Longer Carbon Chain Variants for Perfluoroalkoxylations

Koki Kawai; Sota Ikawa; Naoyuki Hoshiya; Yosuke Kishikawa; Norio Shibata

doi:10.1021/acs.orglett.4c04170

Synthesis of Ngai Reagent and Longer Carbon Chain Variants for Perfluoroalkoxylations

Org Lett. 2024 Dec 20;26(50):11011-11016. doi: 10.1021/acs.orglett.4c04170. Epub 2024 Dec 5.

Authors

Koki Kawai¹, Sota Ikawa¹, Naoyuki Hoshiya², Yosuke Kishikawa², Norio Shibata¹

Affiliations

¹ Department of Nanopharmaceutical Sciences, and Department of Engineering, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya 466-8555, Japan.
² Technology and Innovation Center, DAIKIN Industries, Ltd., 1-1 Nishi-Hitotsuya, Settsu, Osaka 566-8585, Japan.

PMID: 39636164
DOI: 10.1021/acs.orglett.4c04170

Abstract

We present a straightforward method for the synthesis of Ngai trifluoromethoxy reagent and longer carbon chain variants, thereby expanding the range of options for perfluoroalkoxylation reactions. Utilizing cost-effective sodium perfluoroalkane sulfinates (R_fSO₂Na) and N-hydroxylamines, we achieved efficient oxidative cross-coupling reactions facilitated by cerium(IV) ammonium nitrate (CAN) without the need for transition-metal catalysts. The methodology proved effective not only for the synthesis of Ngai-type radical perfluoroalkoxylation reagents but also Qing-type nucleophilic perfluoroalkoxylation reagents.