Total Syntheses of Aromatic Abietane Diterpenoids Utilizing Advances in the Pummerer Rearrangement
Total Syntheses of Aromatic Abietane Diterpenoids Utilizing Advances in the Pummerer Rearrangement
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DOI：
10.1021/acs.orglett.8b02060
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发表时间：
2018-09-21
期刊：
影响因子：
5.2
通讯作者：
Carter, Rich G.
中科院分区：
文献类型：
--
作者：
Li, Xin;Carter, Rich G.
triptobenzene T，vitexifolin C，4-epi-triptobenzene L，triptobenzene L和nepetaefolin F的第一次全合成已经通过对映体选择性的，共同的中间体方法完成，并且已经能够确认和/或建立合成的每个天然产物的绝对立体化学。三个新的和/或未充分利用的Pummerer反应途径的应用证明是至关重要的合成工作。使用脯氨酸磺酰胺催化的Yamada-Otani反应来获得高度官能化的环己烷A环核，包括C-10全碳季立体中心。此外，在C-4烷基化反应中，A环不饱和度对控制立体选择性的重要性也得到了证实。
The first total syntheses of triptobenzene T, vitexifolin C, 4-epi-triptobenzene L, triptobenzene L, and nepetaefolin F have been accomplished through an enantioselective, common intermediate approach and have enabled the confirmation and/or establishment of the absolute stereochemistry of each natural product synthesized. Application of three new and/or underutilized Pummerer reaction pathways proved critical to the synthetic work. A proline sulfonamide-catalyzed Yamada-Otani reaction was used to access the highly functionalized cyclohexane A ring core, including the C-10 all-carbon quaternary stereocenter. Additionally, the importance of the A ring unsaturation for controlling the stereoselectivity during the C-4 alkylation is showcased.