Gold-Catalyzed Enantio- and Diastereoselective Syntheses of Left Fragments of Azadirachtin/Meliacarpin-Type Limonoids

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• 作者：Hang Shi ; Ceheng Tan ; Weibin Zhang ; Zichun Zhang ; Rong Long ; Jianxian Gong ; Tuoping Luo ; Zhen Yang
• 刊名：Journal of Organic Chemistry
• 出版年：2016
• 出版时间：February 5, 2016
• 年：2016
• 卷：81
• 期：3
• 页码：751-771
• 全文大小：996K
• ISSN：1520-6904

文摘

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.