1226985-13-2Relevant academic research and scientific papers
Nickel-catalyzed allylic substitution of simple alkenes
Matsubara, Ryosuke,Jamison, Timothy F.
supporting information; experimental part, p. 1860 - 1875 (2012/02/02)
This report describes a nickel-catalyzed allylic substitution process of simple alkenes whereby an important structural motif, a 1,4-diene, was prepared. The key to success is the use of an appropriate nickel-phosphine complex and a stoichiometric amount of silyl triflate. Reactions of 1-alkyl-substituted alkenes consistently provided 1,1-disubstituted alkenes with high selectivity. Insight into the reaction mechanism as well as miscellaneous application of the developed catalytic process is also documented.
Palladium-catalyzed reactions of 3-substituted methylenecyclopropanes
Shao, Li-Xiong,Li, Jia,Wang, Bao-Yu,Shi, Min
supporting information; experimental part, p. 6448 - 6453 (2011/02/21)
Pd-catalyzed reactions of 3-substituted methylenecyclopropanes (MCPs), in which the substituents can be either hydroxymethyl or formyl, have been thoroughly investigated in the presence or absence of an acid source. It was found that the Pd-catalyzed reactions of methylenecyclopropylcarbinols (Z)-1 in the presence of acetic acid, acetic acid 2-methylene-but-3-enyl esters 4 can be formed in moderate yields. It was also found that Pd alone can catalyze the isomerization of methylenecyclopropylcarbinols (E)-1 in the absence of an acid source to form pent-4-enals 3. The Pd-catalyzed reactions of methylenecyclopropanecarbaldehydes 5 were also carried out in the presence of acetic acid. It was found that when (E)-5 was used as the substrate, the isomerized product, penta-2,4-dienal 6, could be obtained in good to high yields, whereas the use of (Z)-5 gave 2-(3-formylpenta-2,4-dienylidene) cyclopropanecarbaldehyde 7 in moderate to good yields. Plausible mechanisms for all these transformations have been discussed on the basis of the obtained results and control experiments. Copyright
Nickel-catalyzed allylic substitution of simple alkenes
Matsubara, Ryosuke,Jamison, Timothy F.
supporting information; experimental part, p. 6880 - 6881 (2010/07/05)
Nickel-catalyzed intermolecular allylic substitution of simple alkenes (ethylene and alpha olefins) is described. This method is the first catalytic intermolecular process for direct allylation of nonconjugated, nonstrained simple alkenes. Catalyst loadings as low as 2.5 mol % Ni afford the desired product in high yield in both gram-scale and smaller scale coupling reactions.
