Steroidal alkaloids are secondary metabolites mainly isolated from species of Solanaceae and Liliaceae families that occurs mostly as glycoalkaloids. α-chaconine, α-solanine, solamargine and solasonine are among the steroidal glycoalkaloids commonly isolated from Solanum species. A number of investigations have demonstrated that steroidal glycoalkaloids exhibit a variety of biological and pharmacological activities such as antitumor, teratogenic, antifungal, antiviral, among others. However, these are toxic to many organisms and are generally considered to be defensive allelochemicals. To date, over 200 alkaloids have been isolated from many Solanum species, all of these possess the C27 cholestane skeleton and have been divided into five structural types; solanidine, spirosolanes, solacongestidine, solanocapsine, and jurbidine. In this regard, the steroidal C27 solasodine type alkaloids are considered as significant target of synthetic derivatives and have been investigated for more than 10 years in order to obtain new physiologically active steroids. It is important to state that the wide range of biological activities and the low amount available from natural sources, make relevant to obtained these metabolites by synthetic pathway.