118334-49-9Relevant academic research and scientific papers
Alkyliron and Alkylcobalt Reagents, III. - Nonstabilized Ironalkyls: Formation, Detection, and Chemoselectivity
Kauffmann, Thomas,Laarmann, Barbara,Menges, Detlef,Neiteler, Gabriele
, p. 163 - 169 (2007/10/02)
The crystalline ate complex Me4FeLi2(Et2O)2 (1d) described in the literature as well as the complexes MeFeCl (1a), Me2Fe (1b), Me3FeLi (1c), nBu2Fe (2a), nBu4FeLi2 (2b), nOct2Fe (3a), nOct3FeLi (3b), and nOct4FeLi2 (3c) are prepared in situ by transmetallation of MeLi, nBuLi, and nOctLi with FeCl2 (readily available by in situ reduction of FeCl3 with MeLi).All these complexes have been subjected to reaction with organic substrates for the first time.Evidence for this transmetallation has been furnished by a novel test (referred to as "β-bromostyrene-ketone test").In this test, involving addition of β-bromostyrene (4) and 4-methylpentan-2-one (5), the alkyllithium compounds alkylate selectively only the ketone and the alkyliron compounds almost exclusively the β-bromostyrene.The high preference of the alkyliron reagents for the alkylation of the β-bromostyryl residue has been utilized for regioselective butylations and octylations of 1-phenyl>-ethanone (6).Moreover, in competition reactions with benzaldehydes/4-methylpentan-2-one the alkyliron reagents have been found to react usually specifically with aldehydes.The decomposition temperatures of the reagents 1a,b,c and 2b in THF have been determined to be 0, -10, 25, and -20 deg C, respectively.Key Words: Iron, organo reagents
CARBONYLATIVE COUPLING REACTION OF ORGANOFLUOROSILANES WITH ORGANIC HALIDES PROMOTED BY FLUORIDE ION AND PALLADIUM CATALYST
Hatanaka, Yasuo,Fukushima, Satoshi,Hiyama, Tamejiro
, p. 2113 - 2126 (2007/10/02)
Palladium-catalyzed carbonylative cross coupling reaction of organofluorosilanes with organic halides was achieved in the presence of fluoride ion and an atmospheric pressure of carbon monoxide.Alkenyl- or arylfluorosilanes effectively underwent this reaction with alkenyl or aryl iodides in moderate to good yields.Thus, highly functionalized ketones are readily available without protection of reactive functional group such as aldehyde, ketone, ester, nitril, and alcohol.For smooth ketone formation, use of organofluorosilanes is essential; tetraorganosilanes like aryl(trimethyl)silanes, upon reaction with aryl iodides, gave aroyl fluorides instead. Key Words: carbonylative coupling; organofluorosilanes; ketone synthesis
Alkenylfluorosilanes as Widely Applicable Substrates for the Palladium-Catalyzed Coupling of Alkenylsilane/F- Reagents with Alkenyl Iodides
Hatanaka, Yasuo,Hiyama, Tamejiro
, p. 268 - 270 (2007/10/02)
Introduction of fluorine(s) to the silyl groups of alkenylsilanes accelerated the rate of the coupling reaction with alkenyl iodides mediated by fluoride ion and palladium catalyst.The new version of the silicon-based coupling reaction has provided a general and highly stereospecific route to 1,3-dienes as well as alkenylarenes.
