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 PdCl(2)(CH(3)CN)(2), NaI (or PdCl(2)(CH(3)CN)(2) + NaI), and Pd(PPh(3))(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 beta-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.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, P. R. China. masm@mail.sioc.ac.cn
Shengming
S
Ma
Lianghua
L
Lu
Junliang
J
Zhang