Faculty of Chemistry, University of Białystok, ul. Ciołkowskiego 1K, 15-245 Białystok, Poland.
Group of Catalysis, Synthesis and Organic Green Chemistry, Department of Pharmaceutical Sciences, University of Perugia, Via del Liceo 1, 06132 Perugia, Italy.
Int J Mol Sci. 2022 Mar 11;23(6):3022. doi: 10.3390/ijms23063022.
Here we report the reaction in the biphasic system of the in situ prepared selenols and thiols with 1,4-androstadiene-3,17-dione () or prednisone acetate () having α,β-unsaturated ketone as an electrophilic functionalization. The Michael-type addition reaction resulted to be chemo- and stereoselective, affording a series of novel steroidal selenides and sulfides. This is an example of a one-step, eco-friendly process that bypasses some of the main concerns connected with the bad smell and the toxicity of these seleno- and thio-reagents. Furthermore, we demonstrated that the proposed methodology offers the possibility to prepare libraries of steroids variously and selectively decorated with different organochalcogen moieties at the C1 position starting from 1,4-androstadienic skeletons and leaving unaltered the C4-C5 unsaturation. Based on the data reported in the literature the introduction of an organoselenium or an organosulfur moiety in a steroid could provide new interesting pharmaceutically active entities exerting anticancer and antimicrobial activities. In this optic, new synthetic strategies to efficiently prepare this class of compounds could be strongly desirable.
在这里，我们报告了在原位制备的硒醇和硫醇与具有α,β-不饱和酮的 1,4-雄甾二烯-3,17-二酮（）或醋酸泼尼松（）的两相体系中的反应。迈克尔型加成反应具有化学和立体选择性，得到了一系列新型甾体硒化物和硫化物。这是一个一步法、环保的过程的实例，绕过了与这些硒和硫试剂的难闻气味和毒性相关的一些主要问题。此外，我们证明了所提出的方法提供了从 1,4-雄甾烯骨架出发，以各种方式和选择性地在 C1 位用不同的有机杂原子取代基来制备甾体文库的可能性，而不改变 C4-C5 的不饱和性。根据文献中报道的数据，在甾体中引入有机硒或有机硫原子可以提供具有抗癌和抗菌活性的新的有前途的药物活性实体。在这种情况下，高效制备这类化合物的新合成策略可能是非常需要的。
