(n+3)-Cyclization for the Formation of Benzo[7]annulene Derivatives via a [1,4]-Hydride Shift: A Novel Cyclization Mode Involving an Internal Redox Reaction

Jun Nagaki; Tomoko Kawasaki-Takasuka; Keiji Mori

doi:10.1055/a-2287-9391

Synlett, Table of Contents

Synlett 2024; 35(18): 2143-2147
DOI: 10.1055/a-2287-9391

letter

(n+3)-Cyclization for the Formation of Benzo[7]annulene Derivatives via a [1,4]-Hydride Shift: A Novel Cyclization Mode Involving an Internal Redox Reaction

Jun Nagaki

,

Tomoko Kawasaki-Takasuka

,

Keiji Mori ∗

Abstract

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Abstract

We report a unique synthetic route to benzo[7]annulene derivatives. When benzylidene malonates having a 1-(N,N-dialkylamino)alkyl group at the ortho-position are treated with a stoichiometric amount of M(OTf)₃ (M = Sc, Yb, Gd), three transformations ([1,4]-hydride shift/isomerization into an enamine/intramolecular Stork enamine acylation) proceed sequentially to afford various benzo[7]annulene derivatives in moderate chemical yields. To our knowledge, the present reaction is the first example of an internal redox reaction involving a [1,n]-hydride shift/(n+3)-cyclization process.

Key words

C–H bond functionalization - redox process - carbocycles - hydride shift - (n+3)-cyclization - benzo[7]annulene

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References

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Supplementary Material

Supporting Information