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A Concise Enantioselective Total Synthesis of (−)‐Deoxoapodine
Author(s) -
Yoshida Kei,
Okada Kosuke,
Ueda Hirofumi,
Tokuyama Hidetoshi
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202010759
Subject(s) - enantioselective synthesis , aspidosperma , total synthesis , chemistry , phosphoric acid , indole test , alkylation , stereochemistry , tetrahydrofuran , ring (chemistry) , catalysis , organic chemistry , solvent
We have established a highly convergent 10‐step route for the total synthesis of (−)‐deoxoapodine, which is a hexacyclic aspidosperma alkaloid. The quaternary C5 center of the characteristic tetrahydrofuran ring was constructed by a chiral‐phosphoric‐acid‐catalyzed enantioselective bromocycloetherification in a 5‐ endo fashion and subsequent allylation by using the Keck protocol. Construction of the aspidosperma skeleton features the formation of a nine‐membered lactam by a catalytic C−H palladation/alkylation cascade at the indole 2‐position and an iron‐catalyzed oxidative transannular reaction at a late‐stage of the synthesis.