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Synthesis 2012(8): 1258-1262  
DOI: 10.1055/s-0031-1289751
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

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

Dorit Moradova, Abraham Rubinsteina, Dmitri Gelman*b, Morris Srebnik†*a
a School of Pharmacy Institute for Drug Research, The Hebrew University of Jerusalem, P.O. Box 12065, Jerusalem 91120, Israel
Fax: +972(2)6585276; e-Mail: dgelman@chem.ch.huji.ac.il;
b Institute of Chemistry, The Hebrew University of Jerusalem, Edmund Safra Campus, 91904 Jerusalem, Israel
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Publikationsverlauf

Received 9 January 2012
Publikationsdatum:
16. März 2012 (online)

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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.