1-Fluoro-1-sulfonyloxylation of Alkenes by Sterically and Electronically Tuned Hypervalent Iodine: Regression Analysis toward 1,1-Heterodifunctionalization

Masaki Fujie; Kyohei Mizufune; Yoshihiro Nishimoto; Makoto Yasuda

doi:10.1021/acs.orglett.2c04235

1-Fluoro-1-sulfonyloxylation of Alkenes by Sterically and Electronically Tuned Hypervalent Iodine: Regression Analysis toward 1,1-Heterodifunctionalization

Org Lett. 2023 Feb 10;25(5):766-770. doi: 10.1021/acs.orglett.2c04235. Epub 2023 Jan 29.

Authors

Masaki Fujie¹, Kyohei Mizufune¹, Yoshihiro Nishimoto^{1

2}, Makoto Yasuda^{1

2}

Affiliations

¹ Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
² Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.

PMID: 36710445
DOI: 10.1021/acs.orglett.2c04235

Abstract

In the heterodifunctionalization of alkenes, 1,1-regioselectivity remains elusive in sharp contrast to 1,2-regioselectivity. Herein, the 1-fluoro-1-sulfonyloxylation of styrenes with Bu₄NBF₄ and sulfonic acids using a hypervalent iodine ArI(OAc)₂ is reported. Regression analysis of substituents on ArI(OAc)₂ suggested that their electron-withdrawing ability and steric factor influence the 1,1-heterodifunctionalization. We designed o-{2,4-(CF₃)₂C₆H₃}- and p-NO₂-substituted ArI(OAc)₂ by the regression analysis to achieve high selectivity.