Total Synthesis of Zephycarinatines via Photocatalytic Reductive Radicalipso-Cyclization

被引：33

作者：

Takeuchi, Haruka ^{[1
]}

Inuki, Shinsuke ^{[1
]}

Nakagawa, Kohei ^{[1
]}

Kawabe, Takaaki ^{[1
]}

Ichimura, Atsuhiko ^{[1
]}

Oishi, Shinya ^{[1
]}

Ohno, Hiroaki ^{[1
]}

机构：

[1] Kyoto Univ, Grad Sch Pharmaceut Sci, Sakyo Ku, Kyoto 6068501, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 47期

关键词：

alkaloids; natural products; photocatalysis; radicalipso-cyclization; total synthesis; AMARYLLIDACEAE ALKALOID (+)-PLICAMINE; CARBOXYLIC-ACIDS; PHOTOREDOX CATALYSIS; DECARBOXYLATIVE FUNCTIONALIZATION; CASCADE CYCLIZATION; SUPPORTED REAGENTS; AMINO-ACIDS; SPIROCYCLIZATION; ALKYNYLATION; BEARING;

D O I：

10.1002/anie.202009399

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report herein a nonbiomimetic strategy for the total synthesis of the plicamine-type alkaloids zephycarinatines C and D. The key feature of the synthesis is a stereoselective reductive radicalipso-cyclization using visible-light-mediated photoredox catalysis. This cyclization enabled the construction of a 6,6-spirocyclic core structure through the addition of a carbon-centered radical onto the aromatic ring. Biological evaluation of zephycarinatines and their derivatives revealed that the synthetic derivative with a keto group displays moderate inhibitory activity against LPS-induced NO production. This approach could offer future opportunities to expand the chemical diversity of plicamine-type alkaloids as well as providing useful intermediates for their syntheses.

引用

页码：21210 / 21215

页数：6

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