N-Tosyl-linked open-chain yne-ene-yne enediynes 1 and 2 and yne-yne-ene enediynes 3 and 4 have been satisfactorily synthesised. The [2+2+2] cycloaddition process catalysed by the Wilkinson catalyst [RhCl(PPh 3) 3] was tested with the above-mentioned substrates resulting in the production of high yields of the cycloadducts. Enediynes 1 and 2 gave standard [2+2+2] cycloaddition reactions whereas enediynes 3 and 4 suffered β-hydride elimination followed by reductive elimination of the Wilkinson catalyst to give cycloadducts, which are isomers of those that would be obtained by standard [2+2+2] cycloaddition reactions. The different reactivities of these two types of enediyne have been rationalised by density functional theory calculations. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
|Journal||Chemistry - A European Journal|
|Publication status||Published - 16 Dec 2011|
- density functional calculations
- reaction mechanisms