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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 international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202010759
Subject(s) - aspidosperma , enantioselective synthesis , total synthesis , chemistry , indole test , phosphoric acid , alkylation , tetrahydrofuran , stereochemistry , catalysis , ring (chemistry) , 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.