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• Review •

Regioselective Nucleophilic Ring Opening Reactions of Unsymmetric Thiiranes

Zhou Chan, Xu Jiaxi*   

  1. State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, Faculty of Science, Beijing University of Chemical Technology, Beijing 100029, China
  • Received: Revised: Online: Published:
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Thiiranes are a class of important intermediates in organic synthesis, as well in pharmaceutical and agrochemical industries as their oxygen analogs oxiranes and nitrogen analogs aziridines. They have been widely applied in the preparation of sulfur-containing compounds, such as diverse thiols and thioethers and so on, via ring opening reaction and isomerization. Nucleophilic ring opening reactions of unsymmetric thiiranes and their regioselectivity with various widely used nucleophiles are reviewed. Generally, nucleophilic ring opening reactions of unsymmetric thiiranes occur on their less substituted carbon atom, controlled by the steric hindrance. 2-Alkenylthiiranes can undergo an SN2' ring opening reaction in some cases via the attack on the β-carbon atom of their alkenyl group. Strong nucleophiles easily lead to desulfurization of thiiranes to afford the corresponding olefins, while the relatively weak nucleophiles readily result in polymerization of thiiranes, affording polythioethers. In the presence of Lewis acid, the electronic effect affects the regioselectivity in ring opening reactions, even as the prominent effect in the reactions. Although aliphatic thiiranes are still attacked predominantly on their less substituted carbon atom with nucleophiles (the steric hindrance control), aromatic thiiranes and 2-alkenylthiiranes are attacked on their more substituted carbon atom with nucleophiles (the electronic effect control). The current review provides a general rule for the regioselectivity of the nucleophilic ring opening reaction of unsymmetric thiiranes. Contents
1 Introduction
2 Ring opening of thiiranes by carbon nucleophiles
2.1 Ring opening by organometallic reagents
2.2 Ring opening by benzyne
2.3 Ring opening by cyanide
3 Ring opening of thiiranes by nucleophiles in the nitrogen group
3.1 Ring opening by nitrogen-containing nucleophiles
3.2 Ring opening by phosphines
4 Ring opening of thiiranes by nucleophiles in the oxygen group
4.1 Ring opening by oxygen-containing nucleophiles
4.2 Ring opening by sulfur-containing nucleophiles
5 Ring opening of thiiranes by halogen nucleophiles
6 Ring opening of thiiranes by transition metal complexes
7 Ring opening of thiiranes by hydride anion
8 Conclusion and outlook
Key words: thiirane, nucleophile, nucleophilic ring opening reaction, regioselectivity

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