Synlett 2019; 30(17): 1995-1999
DOI: 10.1055/s-0037-1611974
© Georg Thieme Verlag Stuttgart · New York

Thiolate-Initiated Synthesis of Dibenzothiophenes from 2,2′-Bis(methylthio)-1,1′-Biaryl Derivatives through Cleavage of Two Carbon–Sulfur Bonds

Yoshihiro Masuya
Yuki Kawashima
Takuya Kodama
Naoto Chatani*
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan   Email:   Email:
› Author Affiliations
This work was supported by Grant-in-Aid for Scientific Research (18H01978) and Scientific Research on Innovative Area "Precisely Designed Catalysts with Customized Scaffolding" (18H04259) from MEXT, Japan.
Further Information

Publication History

Received: 12 November 2018

Accepted after revision: 11 December 2018

Publication Date:
14 January 2019 (online)


A catalytic reaction involving the cleavage of two carbon–sulfur bonds in 2,2′-bis(methylthio)-1,1′-biaryl derivatives is reported. This reaction does not require a transition-metal catalyst and is promoted by a thiolate anion. Notably, based on DFT calculations, the product-forming cyclization step is shown to proceed through a concerted nucleophilic aromatic substitution (CSNAr) mechanism.

Supporting Information

  • References and Notes

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  • 12 A pathway initiated by a single electron transfer from NaSMe to 1a is unlikely, because this process was found to be endothermic by 66.3 kcal/mol. See Supporting Information for details.

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