Synthetic and computational investigation of neighboring group participation by a nucleophilic disulfide bond

Takuhei Yamamoto; Koki Fukuta; Yuki Kariya; Taiki Matsuura; Hiroaki Hagiwara; Bunji Uno; Yukihiro Esaka

doi:10.1039/d2ob01574a

Synthetic and computational investigation of neighboring group participation by a nucleophilic disulfide bond

Org Biomol Chem. 2022 Dec 21;21(1):65-68. doi: 10.1039/d2ob01574a.

Authors

Takuhei Yamamoto^{1

2}, Koki Fukuta¹, Yuki Kariya¹, Taiki Matsuura¹, Hiroaki Hagiwara³, Bunji Uno⁴, Yukihiro Esaka^{1

2}

Affiliations

¹ Gifu Pharmaceutical University, 1-25-4 Daigaku-nishi, Gifu 501-1196, Japan.
² United Graduate School of Drug Discovery and Medical Information Science, Gifu University, 1-1 Yanaido, Gifu 501-1194, Japan.
³ Department of Chemistry, Faculty of Education, Gifu University, 1-1 Yanaido, Gifu 501-1193, Japan.
⁴ Faculty of Pharmacy, Gifu University of Medical Science, 4-3-3 Nijigaoka, Kani, Gifu 509-0923, Japan.

PMID: 36445233
DOI: 10.1039/d2ob01574a

Abstract

Disulfide bonds of 2-isocyanatophenyl methyl disulfide and 2-endo-isocyanato-6-endo-(methyldisulfanyl)bicyclo[2.2.1]heptane showed neighboring group participation in the formation of thiocarbamates. Natural Bond Orbital (NBO) analyses revealed that the unusual nucleophilicity requires a rigid through-space interaction between a lone pair of the disulfide bond and an antibonding orbital of isocyanate.

Publication types

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