Revisiting Glycosylations Using Glycosyl Fluoride by BF3·Et2O: Activation of Disarmed Glycosyl Fluorides with High Catalytic Turnover

Yoshiyuki Manabe; Takuya Matsumoto; Yuka Ikinaga; Yuya Tsutsui; Shota Sasaya; Yuichiro Kadonaga; Akihito Konishi; Makoto Yasuda; Tomoya Uto; Changhao Dai; Kumpei Yano; Atsushi Shimoyama; Ayana Matsuda; Koichi Fukase

doi:10.1021/acs.orglett.1c03233

Revisiting Glycosylations Using Glycosyl Fluoride by BF₃·Et₂O: Activation of Disarmed Glycosyl Fluorides with High Catalytic Turnover

Org Lett. 2022 Jan 14;24(1):6-10. doi: 10.1021/acs.orglett.1c03233. Epub 2021 Dec 21.

Authors

Yoshiyuki Manabe^{1

2}, Takuya Matsumoto¹, Yuka Ikinaga¹, Yuya Tsutsui³, Shota Sasaya³, Yuichiro Kadonaga^{2

4}, Akihito Konishi^{3

5

6}, Makoto Yasuda^{3

6}, Tomoya Uto¹, Changhao Dai¹, Kumpei Yano¹, Atsushi Shimoyama^{1

2}, Ayana Matsuda¹, Koichi Fukase^{1

2}

Affiliations

¹ Department of Chemistry, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043, Japan.
² Core for Medicine and Science Collaborative Research and Education Project Research Center for Fundamental Sciences Graduate School of Science Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043, Japan.
³ Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
⁴ Division of Science, Institute for Radiation Sciences, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043, Japan.
⁵ Center for Atomic and Molecular Technologies, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
⁶ Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.

PMID: 34932362
DOI: 10.1021/acs.orglett.1c03233

Abstract

Catalytic glycosylations with glycosyl fluorides using BF₃·Et₂O are presented. Glycosylations with both armed and disarmed donors were efficiently catalyzed by 1 mol% of BF₃·Et₂O in a nitrogen-filled glovebox without the use of dehydrating agents. Our finding is in sharp contrast with conventional BF₃·Et₂O-mediated glycosylations, where excess Lewis acid and additives are required. Mechanistic studies indicated that the chemical species formed by the reaction of in situ generated HF and glass vessels are involved in the catalytic cycle.

Publication types

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