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

Citation

Thadkapally, S and Farshadfar, K and Drew, MA and Richardson, C and Ariafard, A and Pyne, SG and Hyland, CJT, Rhodium-catalysed tetradehydro-Diels-Alder reactions of enediynes: Via a rhodium-stabilized cyclic allene, Chemical Science, 11, (40) pp. 10945-10950. ISSN 2041-6520 (2020) [Refereed Article]


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Copyright 2020 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.

DOI: doi:10.1039/d0sc04390g

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.

Item Details

Item Type:Refereed Article
Keywords:Cycloisomerization, oxidation, isoindole
Research Division:Chemical Sciences
Research Group:Organic chemistry
Research Field:Organic chemical synthesis
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the chemical sciences
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
UTAS Author:Pyne, SG (Professor Stephen Pyne)
UTAS Author:Hyland, CJT (Dr Chris Hyland)
ID Code:152219
Year Published:2020
Web of Science® Times Cited:1
Deposited By:CODES ARC
Deposited On:2022-08-15
Last Modified:2022-09-16
Downloads:1 View Download Statistics

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