Low-Temperature Intramolecular [4+2] Cycloaddition of Allenes with Arenes for the Synthesis of Diene Ligands
Dr. Durga Prasad Hari
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 1402, 1015 Lausanne, Switzerland
Present address: School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS UK
These authors contributed equally to this work.
Search for more papers by this authorGuillaume Pisella
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 1402, 1015 Lausanne, Switzerland
These authors contributed equally to this work.
Search for more papers by this authorDr. Matthew D. Wodrich
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 1402, 1015 Lausanne, Switzerland
Search for more papers by this authorArtem V. Tsymbal
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 1402, 1015 Lausanne, Switzerland
Search for more papers by this authorDr. Farzaneh Fadaei Tirani
Institute of Chemistry and Chemical Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC-GE, BCH 2111, 1015 Lausanne, Switzerland
Search for more papers by this authorDr. Rosario Scopelliti
Institute of Chemistry and Chemical Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC-GE, BCH 2111, 1015 Lausanne, Switzerland
Search for more papers by this authorCorresponding Author
Prof. Dr. Jerome Waser
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 1402, 1015 Lausanne, Switzerland
Search for more papers by this authorDr. Durga Prasad Hari
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 1402, 1015 Lausanne, Switzerland
Present address: School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS UK
These authors contributed equally to this work.
Search for more papers by this authorGuillaume Pisella
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 1402, 1015 Lausanne, Switzerland
These authors contributed equally to this work.
Search for more papers by this authorDr. Matthew D. Wodrich
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 1402, 1015 Lausanne, Switzerland
Search for more papers by this authorArtem V. Tsymbal
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 1402, 1015 Lausanne, Switzerland
Search for more papers by this authorDr. Farzaneh Fadaei Tirani
Institute of Chemistry and Chemical Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC-GE, BCH 2111, 1015 Lausanne, Switzerland
Search for more papers by this authorDr. Rosario Scopelliti
Institute of Chemistry and Chemical Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC-GE, BCH 2111, 1015 Lausanne, Switzerland
Search for more papers by this authorCorresponding Author
Prof. Dr. Jerome Waser
Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 1402, 1015 Lausanne, Switzerland
Search for more papers by this authorGraphical Abstract
A highly efficient strategy for the rapid assembly of bicyclooctadienes starting from simple diazo esters and EBX reagents through a one-pot sequential oxyalkynylation/ [4+2] allene-arene cycloaddition reaction at low temperature (23–90 °C) is reported. The obtained products are good chiral ligands for rhodium-catalyzed conjugate addition.
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.
Conflict of interest
The authors declare no conflict of interest.
Supporting Information
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