Functionalization of Methyl (R)-Phenylglycinate Through Orthopalladation: C−Hal, C−O, C−N, and C−C Bond Coupling

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• 作者：Sonia Nieto ; Palmira Arnau ; Elena Serrano ; Rafael Navarro ; Tatiana Soler ; Carlos Cativiela ; Esteban P. Urriolabeitia
• 刊名：Inorganic Chemistry
• 出版年：2009
• 出版时间：December 21, 2009
• 年：2009
• 卷：48
• 期：24
• 页码：11963-11975
• 全文大小：1090K
• 年卷期：v.48,no.24(December 21, 2009)
• ISSN：1520-510X

文摘

The ortho functionalization of methyl R-phenylglycinate has been easily achieved using the known orthopalladated complex [Pd(μ-Cl){R-C₆H₄(CH(CO₂Me)NH₂)-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 X₂ or PhI(OAc)₂ gives XC₆H₄(CH(CO₂Me)NH₂)-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.