Department of Chemistry, University of Georgia, Athens, Georgia 30602, United States.
Org Lett. 2022 Jul 15;24(27):4971-4976. doi: 10.1021/acs.orglett.2c01974. Epub 2022 Jul 7.
Two strategies are described en route to an enantioselective total synthesis of gelsenicine. One approach centers on a chirality transfer cycloisomerization that ultimately fell short. Separately, an asymmetric catalysis route utilizing bisphosphine-gold-catalyzed cycloisomerization was pursued. A catalytic system was identified that provided a synthetic intermediate in our alkaloid syntheses in high enantiopurity and with absolute configuration determined by electronic circular dichroism, thus representing an enantioselective formal total synthesis of (+)-gelsenicine.
本文描述了两种策略，用于对格尔森宁碱进行对映选择性全合成。一种方法侧重于手性转移环化反应，但最终未能成功。另一方面，我们还分别采用了不对称催化途径，利用双膦金催化的环化反应。我们确定了一种催化体系，该体系提供了我们生物碱合成中的一个合成中间体，具有高对映纯度和由电子圆二色性确定的绝对构型，从而代表了（+）-格尔森宁碱的对映选择性全合成。
