First Synthesis of Thiocarbonyl Derivatives of Cage Ketones

Abstract

Thionation of pentacyclo[5.4.0.0 [2] [6] .0 [3] [10] .0 [5] [8] ]undecane-8-one (2) with P₂S₅ in pyridine afforded the corresponding thione 7 in good yield (70%). In contrast to this result, the P₂S₅ promoted thionation of pentacyclo[5.4.0.0 [2] [6] .0 [3] [10] .0 [5] [8] ]undecane-8,11-dione (1) did not afford the expected dithiocarbonyl derivative. Alternatively, reaction of methanolic 1 with H₂S(g)/HCl(g) led to the thiocarbonyl­ derivatives 8 and 9. At longer reaction times (3-5 h), this reaction afforded two unexpected products 10 and 11, both of which are 3,5-disubstituted-4-thiahexacyclo[5.4.1.0 [2] [6] .0 [3] [10] .0 [5] [9] ]-dodecanes.

Key words

cage ketones - thioketones synthesis - sulfur derivative

References

• 1 Eaton PE. Or YS. Branca SJ. Shankar BKR. Tetrahedron  1986,  42:  1621 ; and the preface to the Tetrahedron Symposia-in-print on Synthesis of non-Natural products: Challenge and Reward
• 2a Eaton PE. Cole TW. J. Am. Chem. Soc.  1964,  86:  962 
• 2b Eaton PE. Cole TW. J. Am. Chem. Soc.  1964,  86:  3157 
• 3 Marchand AP. Polycarbocyclic Bridged Ring Compounds, In Rodd’s Chemistry of Carbon Compounds   2nd Supplement to the 2nd Ed., Vols. IIB-E:  Sainsbury M. Elsevier; London: 1994.  Chap. 11. p.227-329  
• 4a Cookson RC. Grundwell E. Hill RR. Hudec J. J. Chem. Soc.  1964,  3062 
• 4b Marchand AP. Allen RW. J. Org. Chem.  1974,  39:  1516 
• 4c Marchand AP. Power TD. Kruger HG. Croat. Chem. Acta  2001,  74:  265 
• 5 Eaton PE. Cassar L. Hudson RA. Hwang DR. J. Org. Chem.  1976,  42:  1445 
• 6 Marchand AP. Aldrichimica Acta  1995,  28:  95 ; and references cited therein
• 7 Lerman BM. Galin FZ. Umansakya LI. Tolstikov GA. Zh. Org. Khim.  1978,  14:  2536 ; Chem. Abstr. 1979, 90, 137330
• 8 Steliou K. Mrani M. J. Am. Chem. Soc.  1982,  104:  3104 
• 9 Barton DHR. Guziec FS. Shahak I. J. Chem. Soc., Perkin Trans. 1  1974,  1794 
• 10 Schweh V. Langhals H. Chem. Ber.  1990,  123:  1981 
• 11 Greidanus JW. Can. J. Chem.  1970,  48:  3530 
• 12a MlostoŇ G. RomaŇski J. Linden A. Heimgartner H. Polish J. Chem.  1996,  70:  595 ; Chem. Abstr. 1996, 125, 86562
• 12b Huisgen R. MlostoŇ G. Pol. J. Chem.  1999,  73:  635 ; Chem. Abstr. 1999, 130, 352041
• 12c Mloston G. Huisgen R. Polborn K. Tetrahedron  1999,  55:  11475 
• 13 Schaumann E. In The Chemistry of Double-Bonded Functional Groups   Supplement A, Vol. 2:  Patai S. Wiley; New York: 1989.  Chap. 17.
• 14a Brillou D. Sulfur Rep.  1992,  12:  297 
• 14b Cava MP. Levinson MI. Tetrahedron  1985,  41:  5061 
• 15 Marchand AP. In Advances in Theoretically Interesting Molecules   Vol. 1:  Thummel RP. JAI; Greenwich: 1989.  p.357-399  
• 16 Marchand AP. Kaya R. J. Org. Chem.  1986,  51:  825