Rhodium-catalysed tetradehydro-Diels-Alder reactions of enediynes: Via a rhodium-stabilized cyclic allene
journal contributionposted on 2023-05-21, 11:43 authored by Thadkapally, S, Farshadfar, K, Drew, MA, Richardson, C, Alireza AriafardAlireza Ariafard, Pyne, SG, Hyland, CJT
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 titleChemical Science
Department/SchoolCollege Office - College of Sciences and Engineering
PublisherRoyal Society of Chemistry
Place of publicationUnited Kingdom
Rights statementCopyright 2020 The Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.