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Zn(OTf)(2)-mediated annulations of N-propargylated tetrahydrocarbolines: divergent synthesis of four distinct alkaloidal scaffolds

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Title: Zn(OTf)(2)-mediated annulations of N-propargylated tetrahydrocarbolines: divergent synthesis of four distinct alkaloidal scaffolds
Authors: Yorimoto, Sadaiwa Browse this author
Tsubouchi, Akira Browse this author →KAKEN DB
Mizoguchi, Haruki Browse this author →KAKEN DB
Oikawa, Hideaki Browse this author →KAKEN DB
Tsunekawa, Yoshiaki Browse this author
Ichino, Tomoya Browse this author
Maeda, Satoshi Browse this author →KAKEN DB
Oguri, Hiroki Browse this author →KAKEN DB
Issue Date: 14-Jun-2019
Publisher: Royal Society of Chemistry
Journal Title: Chemical science
Volume: 10
Issue: 22
Start Page: 5686
End Page: 5698
Publisher DOI: 10.1039/c9sc01507h
Abstract: Intramolecular hydroarylations of N-propargylated tetrahydrocarbolines were efficiently mediated using a unique combination of Zn(OTf) 2 with t-BuOH under neutral conditions. Use of the artificial force induced reaction method in the global reaction route mapping strategy provided insights into the Zn(OTf) 2-mediated hydroarylations and the associated intriguing solvent effects of t-BuOH facilitating a protodezincation process without a Bronsted acid activator. We systematically implemented three distinct hydroarylations as well as an unanticipated a-alkenylation of a carbonyl group to obtain the four alkaloidal scaffolds 2-4, and 18. Zn(OTf) 2-mediated annulation of 1c proceeded through kinetic formation of the spiroindole 3c followed by an alkenyl shift and concomitant retro-Mannich-type fragmentation to furnish azepino[ 4,5-b] indole 2 framework. Substituents on substrate 1 in the vicinity of the reaction sites substantially affected the mode of the divergent annulations. Judicious choices of the substituents, solvent and reaction conditions enabled programmable divergent synthesis of the four distinct skeletons.
Type: article
Appears in Collections:理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

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