金催化的印楝素/米里卡平型柠檬苦素左片段的对映选择性和非对映选择性合成
Gold-Catalyzed Enantio- and Diastereoselective Syntheses of Left Fragments of Azadirachtin/Meliacarpin-Type Limonoids.
作者信息
Shi Hang, Tan Ceheng, Zhang Weibin, Zhang Zichun, Long Rong, Gong Jianxian, Luo Tuoping, Yang Zhen
机构信息
Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Shenzhen Graduate School of Peking University , Shenzhen 518055, China.
State Key Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education and Beijing National Laboratory for Molecular Science (BNLMS), College of Chemistry, and Peking-Tsinghua Center for Life Sciences, Peking University , Beijing 100871, China.
出版信息
J Org Chem. 2016 Feb 5;81(3):751-71. doi: 10.1021/acs.joc.5b02560. Epub 2016 Jan 25.
Meliacarpin-type limonoids are an important class of organic insecticides. Their syntheses are challenging due to their chemical complexity. Here, we report the highly enantio- and diastereoselective synthesis of the left fragments of azadirachtin I and 1-cinnamoylmelianolone, being two important family members of meliacarpin-type limonoids, via pairwise palladium- and gold-catalyzed cascade reactions. Gold-catalyzed reactions of 1,7-diynes were performed as model studies, and the efficient construction of tetracyclic late-stage intermediates was achieved on the basis of this key transformation. Our unique route gave both of the left fragments in 23 steps from the commercially available chiral starting material (-)-carvone. This study significantly advances research on the synthesis of the meliacarpin-type limonoids.
楝果素型柠檬苦素是一类重要的有机杀虫剂。由于其化学结构复杂，它们的合成具有挑战性。在此，我们报道了通过钯和金催化的成对串联反应，对印楝素I和1-肉桂酰米仔兰酮（这是楝果素型柠檬苦素的两个重要家族成员）的左片段进行高度对映选择性和非对映选择性合成。作为模型研究，进行了1,7-二炔的金催化反应，并基于这一关键转化实现了四环后期中间体的高效构建。我们独特的路线从市售手性起始原料（-）-香芹酮出发，经过23步反应得到了两个左片段。这项研究显著推进了楝果素型柠檬苦素合成的研究。
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