Rhodium-catalysed tetradehydro-Diels–Alder reactions of enediynes via a rhodium-stabilized cyclic allene

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 potenti...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2020-09, Vol.11 (40), p.10945-10950
Main Authors: Thadkapally, Srinivas, Farshadfar, Kaveh, Drew, Melanie A., Richardson, Christopher, Ariafard, Alireza, Pyne, Stephen G., Hyland, Christopher J. T.
Format: Article
Language:English
Subjects:
Allene
Aromatic compounds
Catalysis
Chemistry
Crystallography
Diels-Alder reactions
Enediynes
Rhodium
Room temperature
Transition metals
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Summary: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 Rh I -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 Rh I /Rh III /Rh I /Rh III redox cycle involving the formation of an unusual strained 7-membered rhodacyclic allene intermediate and a Rh III -stabilized 6-membered ring allene complex.
ISSN:2041-6520
2041-6539
DOI:10.1039/d0sc04390g