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Palladium catalysed aryl amination reactions in supercritical carbon dioxide. 2005

Catherine J Smith, and Melanie W S Tsang, and Andrew B Holmes, and Rick L Danheiser, and Jefferson W Tester
Melville Laboratory, Department of Chemistry, Lensfield Road, Cambridge, UKCB2 1EW.

Palladium catalysed C-N bond formation in supercritical carbon dioxide has been accomplished. Carbamic acid formation is avoided in part through the use of an N-silylamine as the coupling partner. Employing a catalyst system of Pd2dba3(1 mol%) and 2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl (X-Phos)(2 mol%) enabled the catalytic amination of aryl bromides and chlorides with N-silylanilines to be realised in excellent yield. Extension of the methodology to the N-arylation of N-silyldiarylamines, N-silylazoles and N-silylsulfonamides is reported.

UI MeSH Term Description Entries
D010165 Palladium A chemical element having an atomic weight of 106.4, atomic number of 46, and the symbol Pd. It is a white, ductile metal resembling platinum, and following it in abundance and importance of applications. It is used in dentistry in the form of gold, silver, and copper alloys.
D011312 Pressure A type of stress exerted uniformly in all directions. Its measure is the force exerted per unit area. (McGraw-Hill Dictionary of Scientific and Technical Terms, 6th ed) Pressures
D002245 Carbon Dioxide A colorless, odorless gas that can be formed by the body and is necessary for the respiration cycle of plants and animals. Carbonic Anhydride,Anhydride, Carbonic,Dioxide, Carbon
D002384 Catalysis The facilitation of a chemical reaction by material (catalyst) that is not consumed by the reaction. Catalyses
D006841 Hydrocarbons, Aromatic Organic compounds containing carbon and hydrogen in the form of an unsaturated, usually hexagonal ring structure. The compounds can be single ring, or double, triple, or multiple fused rings. Aromatic Hydrocarbon,Aromatic Hydrocarbons,Hydrocarbon, Aromatic
D000586 Amination The creation of an amine. It can be produced by the addition of an amino group to an organic compound or reduction of a nitro group. Aminations
D000588 Amines A group of compounds derived from ammonia by substituting organic radicals for the hydrogens. (From Grant & Hackh's Chemical Dictionary, 5th ed) Amine
D012821 Silanes Compounds similar to hydrocarbons in which a tetravalent silicon atom replaces the carbon atom. They are very reactive, ignite in air, and form useful derivatives. Silane
D013237 Stereoisomerism The phenomenon whereby compounds whose molecules have the same number and kind of atoms and the same atomic arrangement, but differ in their spatial relationships. (From McGraw-Hill Dictionary of Scientific and Technical Terms, 5th ed) Molecular Stereochemistry,Stereoisomers,Stereochemistry, Molecular,Stereoisomer
D015394 Molecular Structure The location of the atoms, groups or ions relative to one another in a molecule, as well as the number, type and location of covalent bonds. Structure, Molecular,Molecular Structures,Structures, Molecular

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