Molybdenum-Mediated Deconjugation of α,β-Unsaturated Fused-Cyclopentenone Phosphonates

Abstract

The synthesis of diethyl (3-alkyl-5-oxo-4,5,6,6a-tetra­hydro-1H-cyclopenta[c]furan-4-yl)phosphonates from the corresponding 3-allyloxy-1-propynylphosphonates is described. The in situ reaction involves two steps: an intramolecular Pauson-Khand reaction followed by an unusual double bond deconjugation mediated by molybdenum hexacarbonyl in dimethyl sulfoxide.

Key words

double bond isomerization - molybdenum - phosphonate - Pauson-Khand reaction - deconjugation

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32

Different sets of reaction conditions were examined during the optimization studies. We observed that after the formation of intermediate 2, from 1, using two equivalents of Mo(CO)₆ and 10 equivalents of DMSO in toluene at 100 ˚C for one hour, the presence of toluene slowed down the rate of conversion of 2 into 3. Hence, toluene was evaporated at this stage.