Palladium catalysed aryl amination reactions in supercritical carbon dioxide.
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.
Smith
Catherine J
CJ
Melville Laboratory, Department of Chemistry, Lensfield Road, Cambridge, UKCB2 1EW.
Tsang
Melanie W S
MW
Holmes
Andrew B
AB
Danheiser
Rick L
RL
Tester
Jefferson W
JW
D000586:Amination; D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D011312:Pressure; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism
D000588:Amines; D006841:Hydrocarbons, Aromatic; D012821:Silanes; D002245:Carbon Dioxide; D010165:Palladium