Catalytic Regioselectivity Control in Ring-Opening Cycloisomerization of Methylene- or Alkylidenecyclopropyl Ketones

2-Methylene- or alkylidenecyclopropanyl ketones were easily prepared by the regioselective
cyclopropanation of allenes or the reaction of methylene-/alkylidenecyclopropanyllithium with N,N-dimethyl
carboxylic acid amides. Due to the presence of the exo-cyclic CC bond and the strained cyclopropane,
their highly selective ring-opening cycloisomerization using PdCl2(CH3CN)2, NaI (or PdCl2(CH3CN)2 + NaI),
and Pd(PPh3)4 as catalysts provided five different products, i.e., 4H-pyrans, 2,3,4-trisubstituted furans (or
4,5-disubstituted-3-alkylidene-2,3-dihydrofurans), and 2,3,4,5-tetrasubtituted furans (or 2,4,5-trisubstituted-3-alkylidene-2,3-dihydrofurans) in good yields, respectively, depending on the nature of the catalyst and
reaction conditions. The less-substituted CC bonds in these products can be highly selectively
hydrogenated or hydroborated to afford new heterocyclic products stereoselectively. These three types of
different reactions may proceed through a highly regioselective cleavage of a carbon−carbon single bond
in the cyclopropane ring triggered by regioselective halometalation of the CC bond and β-decarbopalladation, halogen anion attack on the nonsubstituted carbon atom of the cyclopropane ring, or the direct
oxidative addition of the distal carbon−carbon single bond of the cyclopropane ring with Pd(0). In some
cases substituent effects were successfully applied to synthesize 2H-pyrans 8 and 3-alkylidene-2,3-dihydrofurans 5, which also provided some mechanistic information.