36359-46-3Relevant academic research and scientific papers
Teaching an old carbocation new tricks: Intermolecular C-H insertion reactions of vinyl cations
Popov, Stasik,Shao, Brian,Bagdasarian, Alex L.,Benton, Tyler R.,Zou, Luyi,Yang, Zhongyue,Houk,Nelson, Hosea M.
, p. 381 - 387 (2018/08/07)
Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramolecular processes. Here we report synthetic and mechanistic studies of vinyl cations generated through silylium-weakly coordinating anion catalysis. We find that these reactive intermediates undergo mild intermolecular carbon-carbon bond-forming reactions, including carbon-hydrogen (C-H) insertion into unactivated sp3 C-H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C-H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives.
Vanadium-catalyzed cross-coupling reactions of alkyl halides with aryl grignard reagents
Yasuda, Shigeo,Yorimitsu, Hideki,Oshima, Koichiro
experimental part, p. 287 - 290 (2009/03/12)
Vanadium(III) chloride catalyzed cross-coupling reactions of alkyl halides with arylmagnesium bromides. Various arylmagnesium bromides, except for an ortho-substituted arylmagnesium reagent, could be used for the reaction. Among alkyl halides tested, cyclohexyl halides and primary alkyl halides were good substrates. The reactions likely proceed via carbon-centered radical intermediates. 2008 The Chemical Society of Japan.
STABILIZED CARBANIONS BY ALKYLLITHIUM-INDUCED DECARBOXYLATION OF NON-ENOLIZABLE CARBOXYLIC ACIDS. AN ANIONIC EQUIVALENT TO THE HUNSDIECKER REACTION
Gilday, John P.,Paquette, Leo A.
, p. 4505 - 4508 (2007/10/02)
Intermediate dianions formed by nucleophilic attac of metyllithium on "alpha"-phenyl or "alpha"- phenylthio carboxylate salts fragment in highly coordinating solvents to produce stabilized carbanions.Once formed, these anions may be conveniently functionalized with various electrophilicreagents.
Cleavage of Carbon-Carbon Bonds with High Stereochemical Control. 5. Course of the Haller-Bauer Reaction of Cyclic α-Phenyl Ketones
Paquette, Leo A.,Ra, Choon Sup
, p. 4978 - 4985 (2007/10/02)
The Haller-Bauer cleavages of three ketones, (R)-(+)-3-benzoyl-3-phenyl-1-isopropylidinecyclopentane (9) and the cis- and trans-1-benzoyl-1-phenyl-4-tert-butylcyclohexanes (16 and 25), have been studied with different base and solvent systems.Whereas the
