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PreprintCC BYChemRxiv

Stereoselective Dearomative [2π+2σ] Cycloadditions of Indoles Enabled by Triplet-State Iminium Ion Reactivity

  • Vasco Corti1
  • Raphael Dollet1
  • Gorka Garay1,2
  • María González Marcos1,3
  • Serafino Mastroianni1
  • Marco Bortolus1
  • Luca Dell’Amico1
  • Luca Dell'Amico
  1. 1Department of Chemical Sciences, University of Padova, Via Marzolo 1, Padova, Italy, 35131
  2. 2Department of Organic and Inorganic Chemistry, University of the Basque Country (UPV/EHU, P.O. Box 644, Bilbao, Spain, 48080
  3. 3Departamento de Química Orgánica, Universidad de Alicante, Ctra. Alicante-San Vicente s/n, Alicante, Spain, 03080
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Abstract

We report an organocatalytic enantioselective [2π+2σ] cycloaddition mediated by visible-light for the dearomatization of indoles. The transformation provides rapid access to complex and sp3-rich indoline-based polycycles with excellent levels of diastereo- and enantiocontrol (up to >20:1 d.r. and 96% ee), through the tripletstate reactivity of a chiral iminium ion. Central to the development of this process was the identification of a suitable chiral primary amine organocatalyst, together with the generation and spectroscopic characterization of the corresponding triplet excited state by time-resolved EPR spectroscopy. The methodology displays broad substrate scope (31 examples) across diverse indoles, bicyclobutanes, and exocyclic alkenes, providing efficient access to highly functionalized bicyclo[2.1.1]hexanes and valuable spirocyclic indoline architectures.

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Cite

BibTeXRIS
BibTeX
@misc{corti2026stereoselective,
  title = {{Stereoselective Dearomative [2π+2σ] Cycloadditions of Indoles Enabled by Triplet-State Iminium Ion Reactivity}},
  author = {Vasco Corti and Raphael Dollet and Gorka Garay and María González Marcos and Serafino Mastroianni and Marco Bortolus and Luca Dell’Amico and Luca Dell'Amico},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008273/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008273/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Stereoselective Dearomative [2π+2σ] Cycloadditions of Indoles Enabled by Triplet-State Iminium Ion Reactivity
AU  - Vasco Corti
AU  - Raphael Dollet
AU  - Gorka Garay
AU  - María González Marcos
AU  - Serafino Mastroianni
AU  - Marco Bortolus
AU  - Luca Dell’Amico
AU  - Luca Dell'Amico
PY  - 2026
DA  - 2026/09/03
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008273/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008273/v1
AB  - We report an organocatalytic enantioselective [2π+2σ] cycloaddition mediated by visible-light for the dearomatization of indoles. The transformation provides rapid access to complex and sp3-rich indoline-based polycycles with excellent levels of diastereo- and enantiocontrol (up to >20:1 d.r. and 96% ee), through the tripletstate reactivity of a chiral iminium ion. Central to the development of this process was the identification of a suitable chiral primary amine organocatalyst, together with the generation and spectroscopic characterization of the corresponding triplet excited state by time-resolved EPR spectroscopy. The methodology displays broad substrate scope (31 examples) across diverse indoles, bicyclobutanes, and exocyclic alkenes, providing efficient access to highly functionalized bicyclo[2.1.1]hexanes and valuable spirocyclic indoline architectures.
ER  -