Indium(III)-catalyzed reductive one-pot synthesis of thioethers from aromatic aldehydes and elemental sulfur

Article abstract of DOI:10.1080/10426507.2015.1036990

Described herein is that a combination of InI3 and 1,1,3,3-tetramethyldisiloxane (TMDS) effectively promotes the reductive thioetherification from aromatic aldehydes with elemental sulfur (S8).

Full text of DOI:10.1080/10426507.2015.1036990

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: http://www.tandfonline.com/loi/gpss20
Indium(Iii)-Catalyzed Reductive One-Pot Synthesis
of Thioethers from Aromatic Aldehydes and
Elemental Sulfur
Takahiro Miyazaki, Kota Nishino, Takeo Konakahara & Norio Sakai
To cite this article: Takahiro Miyazaki, Kota Nishino, Takeo Konakahara & Norio Sakai (2015)
Indium(Iii)-Catalyzed Reductive One-Pot Synthesis of Thioethers from Aromatic Aldehydes and
Elemental Sulfur, Phosphorus, Sulfur, and Silicon and the Related Elements, 190:8, 1378-1379,
DOI: 10.1080/10426507.2015.1036990
To link to this article: http://dx.doi.org/10.1080/10426507.2015.1036990
Accepted online: 09 Apr 2015.
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Date: 04 October 2015, At: 08:22

Phosphorus, Sulfur, and Silicon, 190:1378–1379, 2015
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2015.1036990
INDIUM(III)-CATALYZED REDUCTIVE ONE-POT
SYNTHESIS OF THIOETHERS FROM AROMATIC
ALDEHYDES AND ELEMENTAL SULFUR
Takahiro Miyazaki, Kota Nishino, Takeo Konakahara,
and Norio Sakai
Department of Pure and Applied Chemistry, Faculty of Science and Technology,
Tokyo University of Science (RIKADAI), Noda, Chiba, Japan
GRAPHICAL ABSTRACT
Abstract Described herein is that a combination of InI3 and 1,1,3,3-tetramethyldisiloxane
(TMDS) effectively promotes the reductive thioetherification from aromatic aldehydes with
elemental sulfur (S8).
Keywords Indium; hydrosilane; thioether; benzaldehyde; elemental sulfur
Since thioether derivatives comprising two C-S bonds have constituted a main skele-
ton of biologically or pharmacologically active substances, development of a convenient
and effective synthetic method for thioethers continues occupying one of the most impor-
tant subjects.1 In our previous work, we reported the one-pot sulfidation from carboxylic
acids and thiols by the reducing system comprising 1,1,3,3-tetramethyldisiloxane (TMDS)
and an indium compound such as InBr3 or InI3.2 In this presentation, we report a novel
protocol for the reductive preparation of symmetrical thioethers from aromatic aldehy-
des and elemental sulfur by the reducing system combined with indium(III) iodide and
TMDS.
First, when benzaldehyde and elemental sulfur was treated with 5 mol% of InI3 and
6 equiv (Si-H) of TMDS in 1,2-dichloroethane (1,2-DCE) at 80◦C for 20 h, symmetrical
thioether 1 was obtained in an 82% yield. Then, when benzaldehydes having fluoro, chloro,
and bromo groups at p-position were reacted with elemental sulfur under optimal conditions,
Received 8 January 2015; accepted 30 March 2015.
Address correspondence to Prof. Norio Sakai, Department of Pure and Applied Chemistry, Faculty of
Science and Technology, Tokyo University of Science (RIKADAI), Noda, Chiba 278-8510, Japan. E-mail:
sakachem@rs.noda.tus.ac.jp
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpss.
1378

INDIUM(III)-CATALYZED SYNTHESIS OF THIOETHERS FROM ALDEHYDES AND SULFUR1379
the corresponding thioethers 2–4 were obtained in 78–99% yields. Similarly, the reaction
of p-tolylaldehyde with elemental sulfur produced thioether 5 in 77% yield.
Scheme 1
We also found that when a commercially available thiosilane (Me3SiSSiMe3) was
reacted with p-tolylaldehyde, the expected thioether 5 was formed in 84% yield. Hence,
the result implied that the thiosilane existed as an intermediate in the reductive sulfidation
series.
REFERENCES
1. Nielsen, S.; Nielsen, E. O.; Olsen, G. M.; Liljefors, T.; Peters, D. J. Med. Chem. 2000, 43,
2217–2226.
2. Sakai, N.; Miyazaki, T.; Sakamoto, T.; Yatsuda, T.; Moriya, T.; Ikeda, R.; Konakahara, T. Org.
Lett. 2012, 14, 4366-4369.