Rhodium-Catalyzed Carbonylative Skeleton Rearrangement of 1,4-Enynes Tethered by a Cyclopropane Group

Abstract

The carbonylative skeleton rearrangement of 1,4 enynes tethered by a cyclopropane group proceeded smoothly in the presence of [Rh(CO)₂Cl]₂ under CO atmosphere to give the corresponding 1,2,4,5,6,7-hexahydrocyclopenta[a]inden-3(3bH)-one derivatives in moderate yields.

Key words

rhodium(I) - carbonylation - skeleton rearrangement - 1,4-enyne - cyclopropane

• References and Notes

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Phosphine ligands have great influence on rhodium-catalyzed carbonylation and decarbonylation and a π-acidic phosphine ligand can promote decarbonylation in some cases, see:
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• 21 There is still another mechanism that can explain the formation of product 2a. However, this mechanism involves the formation of a very strained intermediate, which makes this mechanism seems less possible (Scheme 3).

For a similar migration at cyclopentadiene ring, see:
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