- Reductive Elimination to Form C(sp3)-N Bonds from Palladium(II) Primary Alkyl Complexes
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Reductive eliminations to form alkyl-nitrogen bonds are rare, and examples of this reaction from isolated complexes containing simple, unstabilized primary alkyl groups have not been observed. We report the synthesis of stable neopentylpalladium(II) anilido and methyleneamido complexes that undergo reductive elimination to form the C(sp3)-N bonds in N-neopentyl anilines and N-neopentyl imines, respectively. The synthesis and isolation of these complexes were enabled by weak chelation of palladium by P,O ancillary ligands. DFT calculations suggest that neopentylpalladium(II) complexes undergo reductive elimination by a concerted mechanism resembling a migration of the alkyl ligand to the nitrogen either following initial dissociation of the oxygen donor or in concert with lengthening of the Pd-O bond, depending on the identities of the reacting and ancillary ligands.
- Peacock, D. Matthew,Jiang, Quan,Cundari, Thomas R.,Hartwig, John F.
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supporting information
p. 3243 - 3247
(2018/10/05)
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- Catalyst system
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The present invention provides a catalyst system capable of catalyzing the carbonylation of an ethylenically unsaturated compound, which system is obtainable by combining: a) a metal of Group VIB or Group VIIIB or a compound thereof,b) a bidentate phosphine, arsine or stibine ligand, andc) an acid, wherein the ligand is present in at least a 2:1 molar excess compared to the metal or the metal in the metal compound, and that the acid is present in at least a 2:1 molar excess compared to the ligand, a process for the carbonylation of an ethylenically unsaturated compound, a reaction medium, and use of the system.
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Page/Page column 39
(2017/11/17)
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- A bulky biaryl phosphine ligand allows for palladium-catalyzed amidation of five-membered heterocycles as electrophiles
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The incredible bulk: The first palladium-catalyzed amidation of five-membered heterocyclic bromides with multiple heteroatoms was achieved using the Pd/1 catalyst system. N-Arylated imidazoles, pyrazoles, thiazoles, pyrroles, and thiophenes were synthesized in moderate to excellent yield. Experimental results and DFT calculations point to the need for an electron-rich and sterically demanding biaryl phosphine ligand to promote these difficult reactions. Copyright
- Su, Mingjuan,Buchwald, Stephen L.
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supporting information; experimental part
p. 4710 - 4713
(2012/06/18)
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- Production of novel phosphane ligands and use in catalytical reactions
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The invention relates to novel phosphane ligands of formula (Ia) and (Ib): (adamantyl)nP(alkyl)m(1a); (adamantyl)o(Alkyl)qP (alkylen′)P(adamantyl)r(alkyl)s (1b), wherein adamantyl represents an adamantyl radical (IIa, IIb) bonded to the phosphorous atom in position 1 or 2. The invention also relates to the production and use of the above-mentioned ligands in the presence of transitional metal compounds of the 8th. Subgroup of PSE for catalytic reactions, particularly for the refining of halogen aromatics for producing aryl olefins, dienes, diarylene, benzoic acid and acrylic acid derivatives, aryl alkanes and also amines.
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- Ligands for metals and improved metal-catalyzed processes based thereon
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One aspect of the present invention relates to ligands for transition metals. A second aspect of the present invention relates to the use of catalysts comprising these ligands in transition metal-catalyzed carbon-heteroatom and carbon-carbon bond-forming reactions. The subject methods provide improvements in many features of the transition metal-catalyzed reactions, including the range of suitable substrates, reaction conditions, and efficiency.
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- Homogeneous catalysts supported on soluble polymers: Biphasic Sonogashira coupling of aryl halides and acetylenes using MeOPEG-bound phosphine - Palladium catalysts for efficient catalyst recycling
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The Sonogashira coupling of various aryl bromides and iodides with different acetylenes was studied under biphasic conditions with soluble, polymer-modified catalysts to allow the efficient recycling of the homogeneous catalyst. For this purpose, several
- Koellhofer, Axel,Plenio, Herbert
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p. 1416 - 1425
(2007/10/03)
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- Ligands for metals and improved metal-catalyzed processes based thereon
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One aspect of the present invention relates to novel ligands for transition metals. A second aspect of the present invention relates to the use of catalysts comprising these ligands in transition metal-catalyzed carbon-heteroatom and carbon-carbon bond-forming reactions. The subject methods provide improvements in many features of the transition metal-catalyzed reactions, including the range of suitable substrates, reaction conditions, and efficiency.
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- ORGANOPHOSPHORUS COMPOUNDS WITH TERTIARY ALKYL SUBSTITUENTS. VI: A CONVENIENT METHOD FOR THE PREPARATION OF DI-1-ADAMANTYLPHOSPHINE AND DI-1-ADAMANTYLCHLOROPHOSPHINE
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Di-1-adamantylchlorophosphine 3 is obtained by a three step sequence from commercially available adamantane.Despite the bulky 1-adamantyl groups at the phosphorus atom, it reacts readily with water to give di-1-adamantylphosphine oxide 4.Key words: 1-Adamantyl phosphorus compounds, Friedel-Crafts reaction, H/D-exchange, NMR.
- Goerlich, Jens R.,Schmutzler, Reinhard
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p. 211 - 216
(2007/10/02)
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- ORGANOPHOSPHORVERBINDUNGEN MIT TERTIAEREN ALKYLSUBSTITUENTEN. IV. VERSUCHE ZUR P-HALOGENIERUNG VON DI-1-ADAMANTYLPHOSPHIN MIT PHOSGEN, BROM UND IOD
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The reaction of (1-Ad)2PH 1 with C(:O)Cl2, Br2 or I2 furnished solid products of the type +- (X = Cl: 2, Br: 3, I: 4).The identity of the iodo compound 4 was confirmed by elemental analysis.While (1-Ad)2PCl 5 was isolated as a product of the reaction of the chloro compound 2 with NEt3, the corresponding bromo and iodo compounds could not be prepared in a similar fashion.Even prolonged heating of 3 and 4 led only to the formation of mixtures of the phosphonium salts and the monohalophosphines 6 or 7, which could not be separated from the reaction mixture; thus, 6 and 7 were only detected by NMR spectroscopy and by mass spectrometry.Key words: Di-1-adamantylhalophosphines; NMR.
- Goerlich, Jens R.,Schmutzler, Reinhard
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p. 241 - 244
(2007/10/02)
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- Organophosphorus Compounds with Tertiary Alkyl Substituents. III: Synthesis and Reactions of Di-1-adamantyl-Substituted Phosphorus Compounds; Crystal Structure of Di-1-adamantylphosphinic Chloride
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The reaction of adamantane with PCl3/AlCl3, followed by hydrolysis, gave (1-Ad)2P(:O)Cl 1, which was converted to (1-Ad)2P(:O)F 2 and (1-Ad)2P(:S)Cl 3 by standard procedures.The structure of 1 was confirmed by a single crystal X-ray structure determinatio
- Goerlich, Jens R.,Fischer, Axel,Jones, Peter G.,Schmutzler, Reinhard
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p. 801 - 811
(2007/10/02)
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