Reaction of Thiofenchone or Thiochamphor with Disulfur Dichloride: Novel Formation of Tricyclic Polysulfanes

REFERENCES

• Davidson , B. S. , Molinski , T. F. , Barrows , L. R. and Ireland , C. M. 1991 . J. Am. Chem. Soc. , 113 : 4709
   Web of Science ®Google Scholar
• Toste , F. D. and Still , I. W. J. 1995 . J. Am. Chem. Soc. , 117 : 7261
   Web of Science ®Google Scholar
• For reviews, see and Nikonov , G. N. 2008 . Comprehensive Heterocyclic Chemistry III , Vol. Ch. 13.17 , Oxford : Elsevier .
   Google Scholar
• For a review, see and Steudel , R. 2002 . Chem. Rev. , 102 : 3905
   PubMed Web of Science ®Google Scholar
• Okuma , K. , Shiki , K. and Shioji , K. 1998 . Chem. Lett. , 27 : 79
   Google Scholar
• Okuma , K. , Shibata , S. , Shioji , K. and Yokomori , Y. 2000 . Chem. Commun. , : 1535 – 1536 .
   Web of Science ®Google Scholar
• Okuma , K. , Shigetomi , T. , Nibu , Y. , Shioji , K. , Yoshida , M. and Yokomori , Y. 2004 . J. Am. Chem. Soc. , 126 : 9508
   PubMed Web of Science ®Google Scholar
• Shigetomi , T. , Okuma , K. and Yokomori , Y. 2008 . Tetrahedron Lett. , 49 : 36
   Web of Science ®Google Scholar
• Okuma , K. , Nojima , A. , Shigetomi , T. and Yokomori , Y. 2007 . Tetrahedron , 63 : 11748
   Web of Science ®Google Scholar
• Martinez , A. G. , Vilar , E. T. , Moreno , F. and Garcia , A. M. A. 2006 . Tetrahedron: Asymmetry , 17 : 2970
   Google Scholar
• Okuma , K. , Mori , Y. , Tabuchi , M. , Shigetomi , T. and Shioji , K. 2007 . Tetrahedron Lett. , 48 : 8311
   Web of Science ®Google Scholar
• Majchrzak , A. , Mlostoń , G. , Linden , A. and Heimgartner , H. 2004 . Helv. Chem. Acta , 87 : 790
   Web of Science ®Google Scholar
• Synthesis of 6 and 7: To a solution of S2Cl2 (1.5 mmol) in CH2Cl2 was added a solution of 2 (1.0 mmol) in CH2Cl2 at 0°C. After stirring for 5 h, the reaction mixture was evaporated to give pale yellow oil, which was chromatographed over silica gel and then subjected to Gel HPLC to give 6 and 7. Compound 6: yellow oil; 1H NMR (400 MHz, CDCl3): δ 0.87 (s, 3H, CH3), 0.91 (s, 3H, CH3), 1.11 (s, 3H, CH3), 1.28–1.36 (m, 2H, CH2), 1.64–1.70 (m, 1H, CH2), 1.89–1.95 (m, 1H, CH2), 2.56 (d, J = 3.0 Hz, 1H, CH); 13C NMR (100 MHz, CDCl3): 53, 18.71, 18.93, 26.30, 33.24, 53.04, 59.71, 60.02, 129.98, 131.62. Anal. Calcd. for C10H14S4: C, 45.76; H, 5.38%. Found: C, 45.36; H, 5.22%. Compound 7: yellow oil; 1H NMR (400 MHz, CDCl3): δ = 0.74 (s, 3H, CH3), 0.79 (s, 3H, CH3), 1.10 (s, 3H, CH3), 1.49–1.57 (m, 2H, CH2), 1.76–1.82 (m, 1H, CH2), 2.06–2.12 (m, 1H, CH2), 2.64 (d, J = 3.9 Hz, 1H, CH); 13C NMR (101 MHz, CDCl3): δ = 11.95, 18.63, 18.78, 24.99, 31.82, 56.53, 61.54, 61.63, 152.08, 155.86. Anal. Calcd. for C10H14S5: C, 40.78; H, 4.79%. Found: C, 40.70; H, 4.94%.Synthesis of 9: To a solution of selenofenchone (0.086 g, 0.4 mmol) in CH2Cl2 (6 mL) was added a solution of Se2Br2 (0.128 g, 0.4 mmol) in CH2Cl2 (10 mL) at 0°C. After stirring for 30 min, the reaction mixture was filtered, washed with water, dried over MgSO4, and evaporated to give brown solid, which was chromatographed over silica gel by hexane to afford diselenane 9 (0.073 g, 0.17 mmol) along with a small amount of triselenane 10 (0.003 g, 0.6 mmol). Compound 9: yellow crystals, mp 113–114°C; 1H NMR (400 MHz, CDCl3): δ = 0.86 (s, 6H, CH3), 1.01 (s, 6H, CH3), 1.28–1.42 (m, 4 H, CH2), 1.75–1.94 m, 6H, CH2 and CH), 2.04 (br d, 2H, J = 15.6 Hz, CHH), 2.40–2.55 (m, 4H, CH2), 4.86 (br s, 2H, = CH), 5.17 (br S, 2H, ˭CH). 13C NMR (101 MHz, CDCl3) δ = 20.37 (CH3), 20.57 (CH3), 28.84 (CH2), 35.59 (CH2), 37.45 (CH2), 43.27 (CH2), 50.95 (q-C), 61.82 (q-C), 106.38 (˭CH2), 155.73 (˭C). Anal. Calcd. for C20H30Se2: C, 56.08; H, 7.06%. Found: C, 55.71; H, 6.98%. Compound 10 could not be characterized due to its instability. Yellow oil; 1H NMR (400 MHz, CDCl3) δ = 0.89 (s, 6H, CH3), 1.07 (s, 6H, CH3), 1.37–1.42 (m, 4 H, CH2), 1.70–1.80 (m, 4H, CH2), 1.88–2.03 (m, 6H, CH2, and CH), 2.08 (br d, 2H, J = 16.0 Hz, CHH), 2.38–2.56 (m, 4H, CH2), 4.90 (br s, 2H, ˭CH), 5.19 (br S, 2H, ˭CH)
   Google Scholar
• Konstantinova , L. S. and Rakitin , O. L. 2004 . Chem. Rev. , 104 : 2617
   PubMed Web of Science ®Google Scholar
• Crystallographic data for bis(7,7-dimethyl-2-methylenebicylco[2.2.1]heptyl) diselenane 9: FW = C20H30Se2; orthorhombic, Space group; P2(1)2(1)2(1), a = 7.33370(10) Å, b = 12.11700(10) Å, c = 21.8476(2) Å, α = 90°, β = 90°, γ = 90°, Z = 4, Dcalcd = 1.466 Mgm−3; the final R and wR were 0.0260 and 0.0550, respectively, using 20,839 reflections. CCDC-792069 contains the supplementary crystallographic data for this compound. The data can be obtained free of charge at http://www.ccdc.cam.acuk/conts/retrieving.html
   Google Scholar