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Rhodium-catalysed tetradehydro-Diels-Alder reactions of enediynes: Via a rhodium-stabilized cyclic allene

Journal Article


Abstract


  • Efficient methods for the synthesis of fused-aromatic rings is a critical endeavour in the creation of new pharmaceuticals and materials. A direct method for preparing these systems is the tetradehydro-Diels-Alder reaction, however this is limited by the need for harsh reaction conditions. A potential, but underdeveloped, route to these systems is via transition metal-catalysed cycloaromatisation of ene-diynes. Herein, tethered unconjugated enediynes have been shown to undergo a facile room-temperature RhI-catalysed intramolecular tetradehydro-Diels-Alder reaction to produce highly substituted isobenzofurans, isoindolines and an indane. Furthermore, experimental and computational studies suggest a novel mechanism involving an unprecedented and complex RhI/RhIII/RhI/RhIII redox cycle involving the formation of an unusual strained 7-membered rhodacyclic allene intermediate and a RhIII-stabilized 6-membered ring allene complex.

Publication Date


  • 2020

Citation


  • Thadkapally, S., Farshadfar, K., Drew, M. A., Richardson, C., Ariafard, A., Pyne, S. G., & Hyland, C. J. T. (2020). Rhodium-catalysed tetradehydro-Diels-Alder reactions of enediynes: Via a rhodium-stabilized cyclic allene. Chemical Science, 11(40), 10945-10950. doi:10.1039/d0sc04390g

Scopus Eid


  • 2-s2.0-85094670095

Start Page


  • 10945

End Page


  • 10950

Volume


  • 11

Issue


  • 40

Abstract


  • Efficient methods for the synthesis of fused-aromatic rings is a critical endeavour in the creation of new pharmaceuticals and materials. A direct method for preparing these systems is the tetradehydro-Diels-Alder reaction, however this is limited by the need for harsh reaction conditions. A potential, but underdeveloped, route to these systems is via transition metal-catalysed cycloaromatisation of ene-diynes. Herein, tethered unconjugated enediynes have been shown to undergo a facile room-temperature RhI-catalysed intramolecular tetradehydro-Diels-Alder reaction to produce highly substituted isobenzofurans, isoindolines and an indane. Furthermore, experimental and computational studies suggest a novel mechanism involving an unprecedented and complex RhI/RhIII/RhI/RhIII redox cycle involving the formation of an unusual strained 7-membered rhodacyclic allene intermediate and a RhIII-stabilized 6-membered ring allene complex.

Publication Date


  • 2020

Citation


  • Thadkapally, S., Farshadfar, K., Drew, M. A., Richardson, C., Ariafard, A., Pyne, S. G., & Hyland, C. J. T. (2020). Rhodium-catalysed tetradehydro-Diels-Alder reactions of enediynes: Via a rhodium-stabilized cyclic allene. Chemical Science, 11(40), 10945-10950. doi:10.1039/d0sc04390g

Scopus Eid


  • 2-s2.0-85094670095

Start Page


  • 10945

End Page


  • 10950

Volume


  • 11

Issue


  • 40