Dearomative Spirocyclization of Tryptamine-Derived Isocyanides via Iron-Catalyzed Carbene Transfer

Thomas R. Roose, Finn McSorley, Bryan Groenhuijzen, Jordy M. Saya, Bert U. W. Maes, Romano V. A. Orrù, Eelco Ruijter

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Tryptamine-derived isocyanides are valuable building blocks in the construction of spirocyclic indolenines and indolines via dearomatization of the indole moiety. We report the Bu4N[Fe(CO)3NO]-catalyzed carbene transfer of α-diazo esters to 3-(2-isocyanoethyl)indoles, leading to ketenimine intermediates that undergo spontaneous dearomative spirocyclization. The utility of this iron-catalyzed carbene transfer/spirocyclization cascade was demonstrated by its use as a key step in the formal total synthesis of monoterpenoid indole alkaloids (±)-aspidofractinine, (±)-limaspermidine, (±)-aspidospermidine, and (±)-17-demethoxy-N-acetylcylindrocarine.
Original languageEnglish
Pages (from-to)17345-17355
JournalJournal of Organic Chemistry
Volume88
Issue number24
DOIs
Publication statusPublished - 15 Dec 2023

Funding

This work was financially supported by The Netherlands Organisation for Scientific Research (NWO, ECHO) and the Fund for Scientific Research – Flanders (FWO, G0D1921N). B.U.W.M. thanks the Francqui Foundation for an appointment as Collen-Francqui professor. We also kindly thank Elwin Janssen for NMR support and H. Daniel Preschel for HRMS measurements (both VU Amsterdam). This work was financially supported by The Netherlands Organisation for Scientific Research (NWO, ECHO) and the Fund for Scientific Research - Flanders (FWO, G0D1921N). B.U.W.M. thanks the Francqui Foundation for an appointment as Collen-Francqui professor. We also kindly thank Elwin Janssen for NMR support and H. Daniel Preschel for HRMS measurements (both VU Amsterdam).

FundersFunder number
Francqui Foundation
Fund for Scientific Research - Flanders
Fonds Wetenschappelijk OnderzoekG0D1921N
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

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