Selective Synthesis of N-Cyano Sulfilimines by Dearomatizing Stable Thionium Ions

Sang Mee Kim; On-Yu Kang; Hwan Jung Lim; Seong Jun Park

doi:10.1021/acsomega.0c01086

Selective Synthesis of N-Cyano Sulfilimines by Dearomatizing Stable Thionium Ions

ACS Omega. 2020 Apr 22;5(17):10191-10199. doi: 10.1021/acsomega.0c01086. eCollection 2020 May 5.

Authors

Sang Mee Kim^{1

2}, On-Yu Kang^{1

3}, Hwan Jung Lim^{1

4}, Seong Jun Park¹

Affiliations

¹ Department of Drug Discovery, Korea Research Institute of Chemical Technology, 141 Gajeong-ro, Daejeon 34114, Republic of Korea.
² Department of Chemistry, Sogang University, 35 Baekbeom-ro, Mapo-gu, Seoul 04107, Republic of Korea.
³ Department of Chemistry, Sungkyunkwan University, 2066 Seobu-ro, Suwon 16419, Republic of Korea.
⁴ Department of Medicinal and Pharmaceutical Chemistry, University of Science & Technology, 217 Gajeong-ro, Daejeon 34113, Republic of Korea.

Abstract

For the selective synthesis of N-cyano sulfilimines, we have developed a new method based on the soft-soft interaction between thionium ion electrophiles and cyanonitrene nucleophiles. The stable thionium ion was successfully obtained by oxidative dearomatization using phenyliodine (III) diacetate (PIDA) in N,N-dimethylformamide (DMF). The sulfur imination reactions were tolerant to a wide range of functional groups and exhibited high selectivities and excellent yields. The existence of thionium ion intermediates was confirmed by ultraviolet/visible (UV/vis) spectroscopy and ¹H NMR experiments.