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.

cage ketones - thioketones synthesis - sulfur derivative

References

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