Total Syntheses of Cinchona Alkaloids via Photoredox-Catalyzed Deoxygenative Arylation.
Total Syntheses of Cinchona Alkaloids via Photoredox-Catalyzed Deoxygenative Arylation.
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DOI：
10.1021/acs.orglett.3c01659
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发表时间：
2023-06
期刊：
影响因子：
5.2
通讯作者：
Lei Li;Hua-Fei Yang;Qian-Hui Ding;Kun Wei;Yu-Rong Yang
中科院分区：
文献类型：
--
作者：
Lei Li;Hua-Fei Yang;Qian-Hui Ding;Kun Wei;Yu-Rong Yang
醇的金属光氧化还原使能脱氧芳基化是MacMillan最近开发的用于sp2-sp3偶联的稳健合成策略。受此启发，本文首次报道了它在天然产物全合成中的应用，实现了4-溴喹啉或4-溴-6-甲氧基喹啉分别与喹啉或喹啉啶的偶联。通过分子内Diels-Alder反应的关键步骤或Ir/胺双催化烯丙基化反应的对映选择性方式，从头合成了外消旋形式的醇。金鸡纳生物碱的所有成员都可以有效地制备。
Metallaphotoredox-enabled deoxygenative arylation of alcohols is a recently developed robust synthetic strategy for sp2-sp3 coupling by MacMillan. Inspired by this method, we report herein its first utilization in natural product total synthesis through realizing the coupling of 4-bromo-quinoline or 4-bromo-6-methoxyquinoline with quincorine or quincoridine, respectively. The alcohols were de novo synthesized in racemic form by a key step of the intramolecular Diels-Alder reaction or in an enantioselective manner by Ir/amine dual-catalyzed allylation. All members of the cinchona alkaloids could be prepared efficiently.