Development of New Reactions for Synthesis of Cyclopentanoids and their Application

4-环戊烯-1,3-二醇单乙酸酯(1)是合成环戊烷类化合物的理想化合物。然而，由于缺乏将碳亲核试剂安装到环上的有效反应，沿着这条线的使用受到限制。本文基于RMgX和Cu(I)，根据RMgX /Cu(I)的比例和使用的溶剂，开发了S_N2和反S_N2反应的新反应，从而产生4-取代2-环戊烯-1-醇（1,4-异构体）或2-取代3-环戊烯-1-醇（1,2-异构体）。此外，我们还开发了将第二碳亲核试剂连接到上述1,4-异构体上的试剂和条件。我们应用这些反应合成了12-氧基pda、OPC-8:0、OPC-8:0和Δ^<12>-PGJ_2。

4-Cyclopentene-1,3-diol monoacetate (1) is an attractive compound for synthesis of cyclopentanoids. However, the use along this line had been limited due to lack of efficient reactions for installation of carbon nucleophiles onto the ring. Herein, we have developed new reactions based on RMgX and Cu(I) for S_N2 and anti S_N2' reactions, thus producing 4-substituted 2-cyclopenten-1-ols (1,4-isomers) or 2-substituted 3-cyclopenten-1-ols (1,2-isomers) depending on the ratio of RMgZ/Cu(I) and solvent used. In addition, we developed reagents and conditions for attaching second carbon nucleophiles to the 1,4-isomers produced above. We applied these reactions to synthesis of 12-oxo-PDA, OPC-8:0, OPC-8:0, and Δ^<12>-PGJ_2.