Herrmann Pavel, Budesínský Milos, Kotora Martin
Department of Organic and Nuclear Chemistry, and Centre for New Antivirals and Antineoplastics, Faculty of Science, Charles University, Hlavova 8, 128 43 Praha 2, Czech Republic.
J Org Chem. 2008 Aug 15;73(16):6202-6. doi: 10.1021/jo800620d. Epub 2008 Jul 16.
A new and diastereoselective method for the synthesis of the estrone skeleton from a substituted styrene based on sequential 3-fold use of Cp 2ZrBu 2 (oxidative addition-alkylation and two cyclization-alkylation sequences) and a ruthenium complex catalyzed RC-metathesis of a sterically hindered diene was developed. The prepared estratetraene was obtained in 7 steps from a commercially available starting material and thus the overall synthesis of estrone could be accomplished in 9 steps. Moreover, we have also found that the course of the reaction of substrates bearing the 2-halo-1,7-diene moiety with Cp 2ZrBu 2, i.e., cyclization or oxidative addition to the C-X bond, could be controlled by the nature of the halogen leaving group.
基于对Cp₂ZrBu₂的三次连续使用（氧化加成-烷基化以及两个环化-烷基化序列）和钌配合物催化的空间位阻二烯的RC-复分解反应，开发了一种从取代苯乙烯合成雌酮骨架的新的非对映选择性方法。从市售起始原料经7步反应得到制备的雌四烯，因此雌酮的全合成可在9步内完成。此外，我们还发现，带有2-卤代-1,7-二烯部分的底物与Cp₂ZrBu₂反应的过程，即C-X键的环化或氧化加成，可以通过离去卤素基团的性质来控制。
