Low-Temperature Intramolecular [4+2] Cycloaddition of Allenes with Arenes for the Synthesis of Diene Ligands

Durga Prasad Hari; Guillaume Pisella; Matthew D Wodrich; Artem V Tsymbal; Farzaneh Fadaei Tirani; Rosario Scopelliti; Jerome Waser

doi:10.1002/anie.202012299

Low-Temperature Intramolecular [4+2] Cycloaddition of Allenes with Arenes for the Synthesis of Diene Ligands

Angew Chem Int Ed Engl. 2021 Mar 1;60(10):5475-5481. doi: 10.1002/anie.202012299. Epub 2021 Jan 14.

Authors

Durga Prasad Hari^{1

2}, Guillaume Pisella¹, Matthew D Wodrich¹, Artem V Tsymbal¹, Farzaneh Fadaei Tirani³, Rosario Scopelliti³, Jerome Waser¹

Affiliations

¹ Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 1402, 1015, Lausanne, Switzerland.
² Present address: School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.
³ Institute of Chemistry and Chemical Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC-GE, BCH 2111, 1015, Lausanne, Switzerland.

PMID: 33216417
DOI: 10.1002/anie.202012299

Abstract

The intramolecular [4+2] cycloaddition between arenes and allenes first reported by Himbert gives rapid access to rigid polycyclic scaffolds. Herein, we report a one-pot oxyalkynylation/cycloaddition reaction proceeding under mild conditions (23-90 °C) and providing complex polycyclic architectures with high efficiency, and atom and step economy. The bicyclo[2.2.2]octadiene products were obtained with a wide variety of useful functional groups and were successfully applied as chiral ligands for metal catalysis. Computational studies gave a first rationalization of the low activation energy for the cycloaddition based on counter-intuitive favorable dispersive interactions in the transition state.

Keywords: [4+2] cycloaddition; alkynes; diazo compounds; diene ligands; hypervalent iodine reagents.

Abstract

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