Total syntheses of melinonine-E and strychnoxanthine: Evolution of the synthetic strategy enabled by novel method development
Total syntheses of melinonine-E and strychnoxanthine: Evolution of the synthetic strategy enabled by novel method development
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Melinonine-E 和马钱子黄嘌呤的全合成：新方法开发实现合成策略的演变
DOI：
10.1016/j.tet.2018.08.015
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发表时间：
2018-10-04
期刊：
影响因子：
2.1
通讯作者：
Hong, Ran
中科院分区：
文献类型：
--
作者：
Luo, Jisheng;Xie, Changmin;Hong, Ran
在这篇完整的文章中，详细介绍了合成策略的演变，从亚硝基烯环化到用于合成黑碱-e和士的甲氧基鸟嘌呤的aza-Wacker反应。成功地开发了aza-Wacker环化形成桥环的方法，并应用于首次以现成的手性内酯为原料，以5-6步不对称合成了黑melinine - e和士的甲氧嘧啶。根据这两种稀有的β -羰基生物碱的绝对构型，对它们的生物起源进行了修正。此外，aza-Wacker环化的底物范围显示了其访问各种桥环骨架的潜力。机制研究表明，n取代基对酰胺的深远影响是通过可调酰胺化途径成功环化的关键。(C) 2018 Elsevier Ltd.版权所有。
In this full account, the evolution of a synthetic strategy was detailed from a nitroso-ene cyclization to an aza-Wacker reaction for ring construction in the syntheses of melinonine-E and strychnoxanthine. The aza-Wacker cyclization to form the bridged ring was successfully developed and applied in the first asymmetric syntheses of melinonine-E and strychnoxanthine in 5-6 steps from a readily available chiral lactone. The proposed biogenesis of these two rare beta-carbolinium alkaloids was revised based on their absolute configurations. Moreover, the substrate scope of the aza-Wacker cyclization demonstrated its potential for accessing various bridged ring skeletons. The mechanistic investigation established that the profound effect of the N-substituent on the amide was crucial to the success of the cyclization via the tunable amidopalladation pathway. (C) 2018 Elsevier Ltd. All rights reserved.