Premium
Total Synthesis of Zephycarinatines via Photocatalytic Reductive Radical ipso ‐Cyclization
Author(s) -
Takeuchi Haruka,
Inuki Shinsuke,
Nakagawa Kohei,
Kawabe Takaaki,
Ichimura Atsuhiko,
Oishi Shinya,
Ohno Hiroaki
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202009399
Subject(s) - chemistry , stereoselectivity , total synthesis , radical cyclization , photocatalysis , photoredox catalysis , combinatorial chemistry , ring (chemistry) , catalysis , derivative (finance) , organic synthesis , stereochemistry , organic chemistry , financial economics , economics
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 radical ipso ‐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.