Issue 40, 2020

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

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
07 Aug. 2020
Accepted
31 Aug. 2020
First published
04 Sept. 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2020,11, 10945-10950

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

S. Thadkapally, K. Farshadfar, M. A. Drew, C. Richardson, A. Ariafard, S. G. Pyne and C. J. T. Hyland, Chem. Sci., 2020, 11, 10945 DOI: 10.1039/D0SC04390G

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