一價銠金屬催化有機硼酸與掌性環戊烯酮進行共軛加成反應合成前列腺素衍生物

Abstract

本篇論文在探討 (1)利用一價銠金屬作為催化劑，以甲醇當溶劑，氫氧化鉀作為鹼性添加劑，在低溫條件下(3 °C)，催化(R)-47與各種不同芳香基以及烯基硼酸的共軛加成反應，得到單一非鏡像異構物 52。此反應利用於他氟前列素 (tafluprost 3) 的合成。 (2)使用起始物(±)-68利用掌性雙環[2.2.1]配基L1與一價銠金屬形成之催化劑催化與烯基硼酸進行1,4-共軛加成反應，可以得到29−44％的產率以及90−98％的鏡像超越值。

In this thesis, a conjugate reaction of a variety of aryl- and alkenyl- boronic acids, in the presence of 1.5 mol% of [RhCl(COD)]2 catalyst with (R)-47 is described. The conjugate addition reactions conducted at 3 °C, employing 1.2 equiv KOH as the basic additive and using MeOH as the solvent proceeded in a high diastereoselective fashion to give the conjugate adduct in 52−99% yield. In addition, the enantioselective conjugate addition reaction of 68 with 51a, catalyzed by 3 mol% of Rh(I)/L1 was also studied. Compound 79 was obtained as a single diastereomer in 90−98% ee.