Metallkomplexe mit biologisch wichtigen Liganden, CIV [1]. ortho-Palladierte Komplexe von N,N-Dimethyl-C-phenyl-glycinmethylester. Synthese von α-Aminosäure-Derivaten durch Insertion von Isocyaniden, CO, Alkenen und Alkinen in die Pd-C-Bindung / Metal Complexes of Biologically Important Ligands, CIV [ 1]. ortho-Palladated Complexes of N,N-Dimethyl-C-phenylglycine-methylester. Synthesis of α-Amino Acid Derivatives by Insertion of Isocyanides, CO, Alkenes, and Alkynes into the Pd-C Bond

Abstract

Palladium(II) Complexes, ortho-Palladation, N,N-Dimethyl-C-phenylglycine, Insertion Reactions N,N-Dimethyl-C-phenylglycinemethylester reacts with Pd(OAc)2 in acetic acid to give the orthopalladated, acetato bridged complex 1. Treatment of 1 with sodium halide affords the chloro, bromo, and iodo bridged compounds [Me2N C (H )(C 02Me)C6H4PdX]2 (2a -c) (X = halide). From 2a and 1,1 '-bis(diphenylphosphino)ferrocene the phosphine bridged trinuclear complex 3 is obtained. Substitution of the amine ligand of 2a by the phosphino group is observed for the reaction of 2a with Ph2PC(Me)C(Me)PPh2. Insertion of 2,6-dimethyl-phenylisocyanide, CO, alkyl-vinyl-ketones, and diphenylacetylene into the Pd-C bond o f 2a -c provides the ortho substituted organic and organometallic derivatives of phenylglycine 6a -c, 7, 8a -b and 9a -c. The crystal structures of 1, 4a, 6a, 7 and 9a were determined by X-ray diffraction. Sonderdruckanforderungen an Prof. Dr. W. Beck. Röntgenstrukturanalyse. Durch Umsetzung von 1 mit einem Überschuß von Natriumhalogenid erhält man nach säulenchro-0 9 3 9 -5 0 7 5 /9 8 /0 4 0 0 -0 4 4 8 $ 06.00 (c)

Alkenylation of ortho-palladated phenylglycine: synthesis of stilbene derivatives and 3-aryl-isoquinoline-1-carboxylates

“…[30][31][32][33] In this respect, in the last few years there has been increasing interest in the C-H functionalisation of αphenylglycine and some of its derivatives. [34][35][36][37][38][39][40][41][42][43][44][45] However, the C-H functionalisation of amino acids in general, and of α-phenylglycine in particular, is still a difficult task and conditions are far from being simple. [31] One of the main drawbacks of α-phenylglycine is the ease with which is degraded.…”