Olefins, oxidative amination

Unlike the intermolecular reaction, the intramolecular aminopalladation proceeds more easily[13,14,166], Methylindole (164) is obtained by the intramolecular exo amination of 2-allylaniline (163). If there is another olefinic bond in the same molecule, the aminopalladation product 165 undergoes intramolecular alkene insertion to give the tricyclic compound 166[178]. 2,2-Dimethyl-l,2-dihydroquinoline (168) is obtained by endo cyclization of 2-(3,3-dimethyiallyl)aniline (167). The oxidative amination proceeds smoothly... 

Dinitrobenzenesulfenyl chloride is a versatile analytical reagent for the characterization of a wide variety of organic compounds, including alcohols, mercaptans, ketones, olefins, amines, aromatic compounds, olefin oxides, and hydroxysteroids. Review articles summarize these applications.9 10... 

Hosokawa, Murahashi, and coworkers demonstrated the ability of Pd" to catalyze the oxidative conjugate addition of amide and carbamate nucleophiles to electron-deficient alkenes (Eq. 42) [177]. Approximately 10 years later, Stahl and coworkers discovered that Pd-catalyzed oxidative amination of styrene proceeds with either Markovnikov or anti-Markovnikov regioselectivity. The preferred isomer is dictated by the presence or absence of a Bronsted base (e.g., triethylamine or acetate), respectively (Scheme 12) [178,179]. Both of these reaction classes employ O2 as the stoichiometric oxidant, but optimal conditions include a copper cocatalyst. More recently, Stahl and coworkers found that the oxidative amination of unactivated alkyl olefins proceeds most effectively in the absence of a copper cocatalyst (Eq. 43) [180]. In the presence of 5mol% CUCI2, significant alkene amination is observed, but the product consists of a complicated isomeric mixture arising from migration of the double bond into thermodynamically more stable internal positions. 

Niobia-supported MTO has been prepared either by the deposition of sublimed MTO onto the support, or by the impregnation of the support by a solution of MTO, and has been well characterised [54]. A large variety of oxidation reactions were efficiently performed with niobia-supported MTO, such as olefin metathesis catalysis [53,54], reactions of ethyl diazoacetate, heteroatom oxidation (amine and phosphine oxidations) and olefin epoxidation with hydrogen peroxide [55] (Scheme 13). 

Organometallic compounds asymmetric catalysis, 11, 255 chiral auxiliaries, 266 enantioselectivity, 255 see also specific compounds Organozinc chemistry, 260 amino alcohols, 261, 355 chirality amplification, 273 efficiency origins, 273 ligand acceleration, 260 molecular structures, 276 reaction mechanism, 269 transition state models, 264 turnover-limiting step, 271 Orthohydroxylation, naphthol, 230 Osmium, olefin dihydroxylation, 150 Oxametallacycle intermediates, 150, 152 Oxazaborolidines, 134 Oxazoline, 356 Oxidation amines, 155 olefins, 137, 150 reduction, 5 sulfides, 155 Oxidative addition, 5 amine isomerization, 111 hydrogen molecule, 16 Oxidative dimerization, chiral phenols, 287 Oximes, borane reduction, 135 Oxindole alkylation, 338 Oxiranes, enantioselective synthesis, 137, 289, 326, 333, 349, 361 Oxonium polymerization, 332 Oxo process, 162 Oxovanadium complexes, 220 Oxygenation, C—H bonds, 149... 

ALKANOLAMNES - AL KAN OL AMINES FROM OLEFIN OXIDES AND AMMONIA] (Vol 2)... 

Antistatic agents - [ALKANOLAMINES - ALKANOLAMINES FROM OLEFIN OXIDES AND AMMONIA] (Vol 2) - [ALKANOLAMINES - ALKANOLAMINES FROM OLEFIN OXIDES AND AMMONIA] (Vol 2) - [AMINE OXIDES] (Vol 2) - [ANTISTATIC AGENTS] (Vol 3) - [AMINES-FATTY AMINES] (Vol 2) - [PHOSPHORUSCOMPOUNDS](Voll8) -castor oil derivatives as [CASTOR OIL] (Vol 5) -from polyammes pIAMINES AND HIGHER AMINES ALIPHATIC] (Vol 8) -in styrene plastics [STYRENE PLASTICS] (Vol 22) -for textiles [SUGAR ALCOHOLS] (Vol 23)... 

Fabric softeners - [ALKANOLAMOSIES - ALKANOLAMINES FROM OLEFIN OXIDES AND AMMONIA] (Vol 2) - [AMINES - FATTY AMINES] (Vol 2) - [SUGARALCOHOLS] (Vol 23) -from polyamines [DIAMINES AND HIGHER AMINES ALIPHATIC] (Vol 8)... 

A. C. Cope and E. R. Trumbull, "Olefins from Amines. The Flofmann Elimination Reaction and Amine Oxide Pyrolysis," Organic Reactions 11, 317 (1960). 

Oxidative alkoxycarbonylation asymmetric carbonylation, 11, 467 catalyst development, 11, 467 mechanism, 11, 466 Oxidative amination, olefins, 10, 155 Oxidative cleavage, mechanisms, 1, 103 Oxidative promoters, in Pauson-Khand reaction with dicobalt octacarbonyl, 11, 337... 

A Diels-Alder approach to varenicline was recently published by Dr. Reddy s Laboratories. Entry to a key bicyclic intermediate is achieved by an iodide-catalyzed Diels-Alder reaction of tetrabromo dimethyl pyrazine (47) with excess norbomadiene. Dihydroxylation of 48, oxidative cleavage, and reductive amination prepares N-p-methoxybenzyl varenicline (50), which is deprotected under transfer hydrogenation conditions to give varenicline (1) in 10% yield for the sequence.47 This approach continues the theme of building the piperidine of 1 through olefin oxidative cleavage and reductive amination, but by doing so late in the sequence however, the approach... 

Alkylrheniumoxides are known to be versatile, highly active and efficient catalysts for the oxidation of various organic substrates such as olefins, alkynes, amines, ketones, sulfides, or metal carbonyls (a) Hoechst AG (W. A. Herrmann, D. W. Marz, J. G. Kuch-ler, G. Weichselbaumer, R. W. Fischer) DE 3.902.357 (1989) (b) W. A. Herrmann,... 

Cope, A. C., Trumbull, E. R. Olefins from amines the Hofmann elimination reaction and amine oxide pyrolysis. Org. React. 1960,11, 317-493. 

Cope, A. C., Ciganek, E., Howell, C. F., Schweizer, E. E. Amine oxides. VIII. Medium-sized cyclic olefins from amine oxides and quaternary ammonium hydroxides. J. Am. Chem. Soc. 1960, 82,4663-4669. 

Octyl alcohol, 34, 3 -Octyl fluoride, 36, 42 1-Octyl nitrite, 38, 75 Olefins from amine oxides, 39, 41, 42 Oleic acid, 37, 66, 68, 77 39, 15 Oleoyl chloride, 37, 66 Orthocarbonic acid, tetraethyl ESTER, 32, 68... 

The synthesis of N phthaloyl enamides has been reported by a remarkably general method for aerobic oxidative amination of unactivated alkyl olefins as shown in Scheme 9.6 [12]. From a practical synthesis point of view, the phthalimide can not only serve as a directing group for asymmetric hydrogenation but can also be removed under mild conditions. 

Standard Oil Co. (1975) Oil-Soluble Lubricant Bi-Functional Additives from Mannich Condensation Products of Oxidized Olefin Copolymers, Amines and Aldehydes , US Patent 3,872,019. 

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