Solanidane derivatives

Only glycoalkaloids, the aglycones of which are 3P-hydroxy derivatives of solanidane or spirosolane are found in plant foods used for human nutrition. Solanidane derivatives are solanidine (10-44) and demissidine (10-45) and solasodine (10-46), tomatidenol (10-47) and tomatidine (10-48) are derived from spirosolane. 

NOMENCLATUBE. The relationships in the steroids which find many counterparts in numerous solanidine derivatives suggest a rational nomenclature based on that of the steroids. The oxygen-free saturated compound V serves as the basic skeleton and is termed solanidane. This terminology will be used here, adopting the latest principles of steroid nomenclature (63). Instead of the earlier terms cis-, trans-, and alio-, the letters a, and J will be used to indicate configuration in the same way that they are used in the steroid group. 

Another route by which rubijervine is convertible into known solanidine derivatives is by way of the saturated diol V, which was first oxidized with chromic acid in acetic acid to the diketone (XIV), the bis(semi-carbazone) of which on Wolff-Kischner reduction afforded a mixture of 3/3-solanidanol (IX, p. 256) and solanidane (V, p. 256) (57). Dehydrogenation of rubijervine with selenium gave the typical dehydrogenation... 

Thus, the C27-steroid alkaloids with C-nor-D-homo [14(13->-12)-abeo] ring system, that is, with a jervane (5) or cevane (6) skeleton, found in Liliaceae but until now not in Solanaceae, are not included they will be described exhaustively in another chapter of this volume by S. M. Kupchan. On the other hand, the tertiary Veratrum bases rubijervine, isorubijervine, and veralobine belong to the solanidanes and will be mentioned briefly in this chapter, but a detailed description of these alkaloids and their derivatives will also be given by S. M. Kupchan. 

As already described in Section IV,B, the A-chloro derivatives of the 16-unsubstituted(22i2 25(8)-and (22 S 25iJ)-22,26-epimino-5a-cholestan-3 -ols smoothly afford the corresponding solanidanes by photochemically induced Hofmann-Loffler-Freytag cyclization employing similar re-... 

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