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.
Highlights
New methods for the construction of functionalized aromatic rings is an important area of research due to their wide occurrence in bioactive molecules and materials
Efficient methods for the synthesis of fused-aromatic rings is a critical endeavour in the creation of new pharmaceuticals and materials
The tetradehydro-Diels–Alder (TDDA) reaction of polyunsaturated enediyne systems is of particular note as it allows for the direct formation of a benzenoid ring in a single step, via an intriguing high energy cyclic allene intermediate, which typically aromatises via a hydride shi (Scheme 1a).[2,3]
Summary
New methods for the construction of functionalized aromatic rings is an important area of research due to their wide occurrence in bioactive molecules and materials. 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.
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