Synthesis of Symmetrical and Unsymmetrical 1,4-Dithiins by Rhodium-Catalyzed Sulfur Addition Reaction to Alkynes

Mieko Arisawa; Takuya Ichikawa; Saori Tanii; Masahiko Yamaguchi

doi:10.1055/s-0035-1561452

Synthesis, Table of Contents

Synthesis 2016; 48(18): 3107-3119
DOI: 10.1055/s-0035-1561452

paper

Synthesis of Symmetrical and Unsymmetrical 1,4-Dithiins by Rhodium-Catalyzed Sulfur Addition Reaction to Alkynes

Mieko Arisawa*

Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Sendai, 980-8578, Japan Email: yama@m.tohoku.ac.jp Email: arisawa@m.tohoku.ac.jp

,

Takuya Ichikawa

Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Sendai, 980-8578, Japan Email: yama@m.tohoku.ac.jp Email: arisawa@m.tohoku.ac.jp

,

Saori Tanii

Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Sendai, 980-8578, Japan Email: yama@m.tohoku.ac.jp Email: arisawa@m.tohoku.ac.jp

,

Masahiko Yamaguchi*

Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba, Sendai, 980-8578, Japan Email: yama@m.tohoku.ac.jp Email: arisawa@m.tohoku.ac.jp

› Author Affiliations

Abstract

All articles of this category

Abstract

A convenient synthetic method for 1,4-dithiins was developed using sulfur and alkynes. A rhodium complex catalyzes the addition reaction of sulfur with cyclic alkynes giving the corresponding symmetrical 1,4-dithiines under reflux conditions in 2-butanone. Unsymmetrical 1,4-dithiins are synthesized by the reaction of sulfur with dialkyl acetylenedicarboxylates in the presence of cyclic alkynes or vinyl ethers.

Key words

sulfur - 1,4-dithiins - rhodium - addition reaction - alkynes

Full Text

References

References

Inhibitor of the ATM kinase:

1a Lau A, Swinbank KM, Ahmed PS, Taylor DL, Jackson SP, Smith GC. M, O’Connor MJ. Nat. Cell Biol. 2005; 7: 493
1b Hickson I, Zhao Y, Richardson CJ, Green SJ, Martin NM. B, Orr AI, Reaper PM, Jackson SP, Curtin NJ, Smith GC. M. Cancer Res. 2004; 64: 9152

2 Takatani T, Ogino T, Masugi T, Tsuji K. Jpn Kokai Tokkyo Koho JP 54128594 A, 1979

3a Munakata M, Yan SG, Ino I, Kuroda-Sowa T, Maekawa M, Suenaga Y. Inorg. Chim. Acta 1998; 271: 145
3b Kacholdt H, Berges P, Klar G. Transition Met. Chem. 1987; 12: 515
3c Behrens U, Berges P, Bieganowski R, Hinrichs W, Schiffling C, Klar G. J. Chem. Res., Synop. 1986; 326
3d Crabtree RH, Davis MW, Mellea MF, Mihelcic JM. Inorg. Chim. Acta 1983; 72: 223
3e Kwik W.-L, Tan S.-F. J. Chem. Soc., Dalton Trans. 1976; 1072

LED materials using thianthrene unit:

4a Suzuki Y, Murakami K, Ando S, Higashihara T, Ueda M. J. Mater. Chem. 2011; 21: 15727
4b Friedrich R, Janietz S, Wedel A. Macromol. Chem. Phys. 1999; 200: 731
4c Friedrich R, Janietz S, Wedel A. Macromol. Chem. Phys. 1999; 200: 739

Thiophene-condensed organic field-effect transistors:

5a Ito H, Watanabe D, Yamamoto T, Tsushima N, Muraoka H, Ogawa S. Chem. Lett. 2013; 42: 646
5b Yamamoto T, Ogawa S, Sato R. Tetrahedron Lett. 2004; 45: 7943

Coloring material:

5c Sahin E, Camurlu P, Toppare L. Synth. Met. 2006; 156: 124

Use of 1,4-dithiin-2,3:5,6-tetrayl diimide:

5d Gaina C, Gaina V. Des. Monomers Polym. 2005; 8: 347

6a Review: Sato R. In Science of Synthesis . Vol. 16. Yamamoto Y. Thieme; Stuttgart: 2004: 57
6b Baker RH, Barkenbus C. J. Am. Chem. Soc. 1936; 58: 262
6c Meijer J, Vermeer P, Verkruijsse HD, Brandsma L. Recl. Trav. Chim. Pays-Bas 1973; 92: 1326
6d Montevecchi PC, Tundo A. J. Org. Chem. 1981; 46: 4998
6e Skabara PJ, Berridge R, Prescott K, Goldenberg LM, Ortí E, Viruela R, Pou-Amérigo R, Batsanov AS, Howard JA. K, Coles SJ, Hursthouse MB. J. Mater. Chem. 2000; 10: 2448

7 Nakayama J, Yomoda R, Hoshino M. Heterocycles 1987; 26: 2215
8 Adam W, Fröhling B, Weinkötz S. J. Org. Chem. 1998; 63: 9154
9 Nakayama J, Kashiwagi M, Yomoda R, Hoshino M. Nippon Kagaku Kaishi 1987; 1424

10a Dzhemilev UM, Baibulatova NZ, Tkachenko TK, Kunakova RV, Khalilov LM, Berg AA. Izv. Akad. Nauk. SSSR. Ser. Khim. 1989; 3: 655

Reaction of cycloalkynes were reported in a patent:

10b Dzhemilev UM, Shajbakova MG, Makhmudijarov GA, Ibragimov AG, Starikova ZA, Antipin MJ, Khalilov LM. Russian Patent RU 2436783, C2, 20111220, 2011

11a Nakayama J, Shimomura M, Iwamoto M, Hoshino M. Heterocycles 1985; 23: 1907
11b Kobayashi K, Mutai K, Kobayashi H. Tetrahedron Lett. 1979; 20: 5003

12 Arisawa M, Ichikawa T, Yamaguchi M. Chem. Commun. 2015; 51: 8821
13 CCDC 1445540 contains the supplementary crystallographic data for endo-3b in this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.

14a Ouch K, Mashuta MS, Grapperhaus CA. Eur. J. Inorg. Chem. 2012; 475
14b Harrison DJ, Nguyen N, Lough AJ, Fekl U. J. Am. Chem. Soc. 2006; 128: 11026
14c Kajitani M, Suetsugu T, Wakabayashi R, Igarashi A, Akiyama T, Sugimori A. J. Organomet. Chem. 1985; 293: C15
14d The reaction of rhodium dithiolene complex CpRh(S₂C₂R₂) (R = CO₂Et) with 1a was conducted under refluxing 2-butanone; 1,4-dithine and thiophene were not formed.

15 Bühl H, Timm U, Meier H. Chem. Ber. 1979; 112: 3728
16 Draber W. Chem. Ber. 1967; 100: 1559
17 Sun D.-Q, Yang J.-K. J. Heterocycl. Chem. 2012; 23: 84
18 Ngounda M, Bozec HL, Dixneuf P. J. Org. Chem. 1982; 47: 4000

Supplementary Material

Supporting Information