Rosset Isac G, Dias Rafael M P, Pinho Vagner D, Burtoloso Antonio C B
Instituto de Química de São Carlos, Universidade de São Paulo , CEP 13560-970, São Carlos, SP Brazil.
J Org Chem. 2014 Jul 18;79(14):6748-53. doi: 10.1021/jo5011558. Epub 2014 Jul 8.
A straightforward and stereoselective synthesis of the alkaloid preussin is described starting from decanal and diethyl 3-diazo-2-oxopropylphosphonate. The key steps are an aza-Michael reaction from an α,β-unsaturated diazoketone followed by a highly stereoselective Cu-catalyzed ylide formation and then a [1,2]-Stevens rearrangement. This strategy is feasible for extension to preussin analogues, demonstrating its utility for the rapid construction of all-cis-substituted pyrrolidines.
本文描述了一种从癸醛和3-重氮-2-氧代丙基膦酸二乙酯出发，直接且立体选择性地合成生物碱普瑞辛的方法。关键步骤包括α,β-不饱和重氮酮的氮杂迈克尔反应，随后是高度立体选择性的铜催化叶立德形成，然后是[1,2]-史蒂文斯重排。该策略可扩展至普瑞辛类似物，证明了其在快速构建全顺式取代吡咯烷方面的实用性。
