Functionalization of methyl (R)-phenylglycinate through orthopalladation: C-Hal, C-O, C-N, and C-C bond coupling.
The ortho functionalization of methyl R-phenylglycinate has been easily achieved using the known orthopalladated complex [Pd(mu-Cl){R-C(6)H(4)(CH(CO(2)Me)NH(2))-2}](2) (1) as synthetic tool. Different functional groups have been introduced at the ortho position of the aryl ring. The reaction of (R)-1 with X(2) or PhI(OAc)(2) gives XC(6)H(4)(CH(CO(2)Me)NH(2))-2 (X = I, Br, OMe, OEt) through oxidative coupling, while the reaction with CO gives an isoindolone. (R)-1 also reacts with one, two, or three alkyne molecules to give different metal-containing or metal-free heterocycles. The resulting functionalized amino esters or heterocycles retain the chirality of (R)-1, according with the values of the optical rotation and the obtained ee values ranging from 22%-87%. The X-ray structures of six representative compounds have also been determined.
Nieto
Sonia
S
Departamento de Compuestos Organometálicos, Instituto de Ciencia de Materiales de Aragón, CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza, Spain.
Arnau
Palmira
P
Serrano
Elena
E
Navarro
Rafael
R
Soler
Tatiana
T
Cativiela
Carlos
C
Urriolabeitia
Esteban P
EP
D002244:Carbon / Q000737:chemistry; D018360:Crystallography, X-Ray; D005998:Glycine / Q000031:analogs & derivatives* / Q000737:chemistry; D006219:Halogens / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009584:Nitrogen / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism
D006219:Halogens; D009942:Organometallic Compounds; C033393:methyl phenylglycine; D010165:Palladium; D002244:Carbon; D009584:Nitrogen; D010100:Oxygen; D005998:Glycine