118097-60-2Relevant articles and documents
Imidazole derivatives as accelerators for ruthenium-catalyzed hydroesterification and hydrocarbamoylation of alkenes: Extensive ligand screening and mechanistic study
Konishi, Hideyuki,Muto, Takashi,Ueda, Tsuyoshi,Yamada, Yayoi,Yamaguchi, Miyuki,Manabe, Kei
, p. 836 - 845 (2015/03/14)
Imidazole derivatives are effective ligands for promoting the [Ru3(CO)12]-catalyzed hydroesterification of alkenes using formates. Extensive ligand screening was performed to identify 2-hydroxymethylated imidazole as the optimal ligand. Neither carbon monoxide gas nor a directing group was required, and the reaction also showed a wide substrate generality. The Ru-imidazole catalyst system also promoted intramolecular hydrocarbamoylation to afford lactams. A Ru-imidazole complex was unambiguously analyzed by X-ray crystallography, and it had a trinuclear structure derived from one [Ru3(CO)12] and two ligands. This complex was also successfully used for hydroesterification. The mechanism was examined in detail by using D- and 13C-labeled formates, indicating that the hydroesterification reaction proceeds by a decarbonylation-recarbonylation pathway. Effective imidazole assistant: [Ru3(CO)12]-catalyzed hydroesterification of alkenes by using formates is drastically accelerated by imidazole derivatives and exhibits a broad substrate scope for both alkenes and formates. The Ru-imidazole complex also catalyzes the intramolecular hydrocarbamoylation of alkenes.
Remarkable improvement achieved by imidazole derivatives in ruthenium-catalyzed hydroesterification of alkenes using formates
Konishi, Hideyuki,Muto, Takashi,Manabe, Kei,Ueda, Tsuyoshi
supporting information, p. 4722 - 4725,4 (2012/12/12)
Imidazole derivatives are revealed to be effective ligands in the Ru-catalyzed hydroesterification of alkenes using formates, affording one-carbonelongated esters in high yields. Further, intramolecular hydroesterification was successfully performed to give lactones for the first time. Imidazole derivatives can contribute to promote the reaction as well as to suppress the undesired decarbonylation of formate. Toxic CO gas, a directing group, and large excess alkenes are not required.
ORGANOCOPPER-IODOSILANE COMBINATIONS IN CONJUGATE ADDITIONS
Bergdahl, Mikael,Lindstedt, Eva-Lotte,Nilsson, Martin,Olsson, Thomas
, p. 535 - 544 (2007/10/02)
This paper concerns new possibilities opened by the addition of (mono)organocopper compounds and iodotrimethylsilane (TMSI) to α,β-unsaturated ketones and esters giving the silyl enol ethers and ketene acetals, respectively.We demonstrate the homogeneous addition of methylcopper-tributyl-phosphine-iodotrimethylsilane to methyl cinnamate, the use of organocopper-bromotrimethylsilane combinations, the dominating formation of Z-silyl enol ethers on conjugate addition of methyl- and butylcopper/TMSI to benzalacetone, and the formation of silyl enol ethers in other additions of organocopper compounds and TMSX to conjugated ketones.The Z-selectivity for addition to benzalacetone corresponds to s-cis conformations in ?-complexes between copper(I) chloride and 1-penten-3-one or 3-buten-2-one.The stereoselectivity could support a reaction path via ?-complexes between organocopper-iodotrimethylsilane complexes and s-cis conformers of the substrates.
