Diastereoselective Synthesis of cis- and trans- Annulated Hexahydrothioxanthenes: The First Stereochemical Study on the Intramolecular Polar Cycloaddition of Cationic 2 - Thiabutadienes

Synlett

Volumn 1996, Issue 4, 1996, Pages 396-398

  Beifuss, Uwe ^a   Gehm, Henning ^a   Taraschewski, Michael ^a  

^a UNIVERSITY OF GÖTTINGEN   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 1542739549     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1996-5408     Document Type: Article

References (21)

1. Smit, W.A.; Ibragimov, M.A. In Chemistry of Organosulfur Compounds: General Problems; Belen'kii, L.I., Ed.; Ellis Horwood: Chichester, 1990; p 141.
2. Claus, P.K. In Houben-Weyl, 4th ed., Vol. E 11; Klamann, D., Ed.; Thieme: Stuttgart, 1985; p 1469.
3. De Lucchi, O.; Miotti, U.; Modena, G. Org. React. 1991, 40, 157.
4. Boger, D.L.; Weinreb, S.N. Hetero Diets-Alder Methodology in Organic Synthesis; Academic Press: San Diego, 1987.
5. (a) Ishibashi, H.; Nakatani, H.; Choi, D.J.; Taguchi, M.; Ikeda, M. Chem. Pharm. Bull. 1990, 38, 1738;
6. (b) Tamura, Y.; Ishiyama, K.; Mizuki, Y.; Maeda, H.; Ishibashi, H. Tetrahedron Lett. 1981, 22, 3773.
7. 13C NMR, and MS) data were obtained for all new compounds.
8. Böhme, H.; Fischer, H.; Frank, R. Liebigs Ann. Chem. 1949, 563, 54.
9. Schmidt, R.R. Angew. Chem. 1973, 85, 235; Angew. Chem., Int. Ed. Engl. 1973, 12, 212.
10. Schmidt, R.R. Angew. Chem. 1973, 85, 235; Angew. Chem., Int. Ed. Engl. 1973, 12, 212.
11. (a) Sato, T.; Otera, J.; Nozaki, H. J. Org. Chem. 1990, 55, 6116,
12. cit. lit.; (b) Mori, I.; Bartlett, P.A.; Heathcock, C.H. J. Org. Chem. 1990, 55, 5966.
13. Calculations were performed using the VAMP and MOPAC 6.0 packages. VAMP (Clark, T., Universität Erlangen-Nürnberg) is a vectorized version of AMPAC and MOPAC.
14. 1x), 3.71 (q, J = 3.5 Hz, 1H, 4a-H), 4.01 (d, J = 4.0 Hz, 1H, 9-H), 6.73 (dt, J = 1.5 Hz, J = 7.5 Hz, 1H, 7-H), 6.88 (mc, 1H, 6-H), 7.00 (dt, J = 1.5 Hz, J = 7.5 Hz, 1H, 8-H), 7.06 (dd, J = 1.5 Hz, J = 7.5 Hz, 2H, 2′-H, 6′-H), 7.11 (tt, J = 1.5 Hz, J = 7.5 Hz, 1H, 4′-H), 7.17 (dt, J = 1.5 Hz, J = 7.5 Hz, 2H, 3′-H, 5′-H), 7.24 (dd, J = 1.5 Hz, J = 8.0 Hz, 1H, 5-H).
15. exo/endo, orientation of the chain relative to the heterodiene; E/Z, configuration of the C,S-double bond of the 2-thiabutadiene; syn/anti, orientation of the hydrogens at the prochirality centers between which a C,C-bond is formed; see also: Tietze, L.F.; Brand, S.; Brumby, T.; Fennen, J. Angew. Chem. 1990, 102, 675; Angew. Chem., Int. Ed. Engl. 1990, 29, 665.
16. exo/endo, orientation of the chain relative to the heterodiene; E/Z, configuration of the C,S-double bond of the 2-thiabutadiene; syn/anti, orientation of the hydrogens at the prochirality centers between which a C,C-bond is formed; see also: Tietze, L.F.; Brand, S.; Brumby, T.; Fennen, J. Angew. Chem. 1990, 102, 675; Angew. Chem., Int. Ed. Engl. 1990, 29, 665.
17. eq), 1.90 (ddt, J = 3.5 Hz, J = 10.5 Hz, J = 11.0 Hz, 1H, 9a-H), 2.85 (ddd, J = 4.0 Hz, J = 11.0 Hz, J = 12.0 Hz, 1H, 4a-H), 3.3 (d, J = 10.5 Hz, 1H, 9-H), 6.66-6.72 (m, 2H, 7-H, 8-H), 6.82 (mc, 1H, 6-H), 6.95-6.98 (m, 2H, 2′-H, 6′-H), 7.05 (tt, J = 2.0 Hz , J = 1.5 Hz, 1H, 4′-H), 7.11 (mc, 2H, 3′-H, 5′-H), 7.20 (dd, J = 2.0 Hz, J = 7.5 Hz, 1H, 5-H).
18. Typical Experimental Procedure: 2,6-Lutidine (0.07 mL, 0.6 mmol) and TFAA (0.28 mL, 2.0 mmol) were successively added to a stirred solution of 18 (299 mg, 1.0 mmol) in dichloromethane (10 mL) under argon at 0°C. The reaction mixture was stirred for 3 h at 0°C and 16 h at 25°C. After quenching the reaction by addition of water (10 mL) and extraction with dichloromethane (3 × 10 mL) the combined organic layers were dried over sodium sulfate, the solvent was removed in vacuo and the residue was purified by flash chromatography on silica gel (acetone / petrolether = 1:100) to yield 266 mg (89%) of a mixture of diastereomers. Crystallization from pentane / tetrachloromethane gave pure 7 (mp. 145°C).
19. A solution of (Z)-methyl styrene in dichloromethane was stirred with a) 2.0 equiv. TFAA and 0.6 equiv. 2,6-lutidine at 0°C for 48 h and b) 5.0 equiv. TFAA and 2.4 equiv. 2,6-lutidine at - 20°C for 48 h. In both cases no isomerization of the (Z)-double bond was observed.
20. Domino reactions: Tietze, L.F.; Beifuss, U. Angew. Chem. 1993, 105, 137; Angew. Chem., Int. Ed. Engl. 1993, 32, 131.
21. Domino reactions: Tietze, L.F.; Beifuss, U. Angew. Chem. 1993, 105, 137; Angew. Chem., Int. Ed. Engl. 1993, 32, 131.