Sonia Nieto

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.

Orthometallation as a Strategy in Pd-mediated Organic Synthesis

The orthopalladated complexes are among the most representative Pd(II) compounds. They display a wide prospect of applications, but they are mainly known by their use as intermediates in metal-mediated organic synthesis. In this review we describe how palladacycles are used to build up new molecules through regioselective formation of C-halogen, C-O, C-N, C-P, C-S and C-C bonds, either under catalytic or stoichiometric conditions. This methodology is based on the selective incorporation of the Pd into the organic skeleton to be modified and subsequent reactivity of the Pd-C bond toward different substrates. In many cases this strategy is alternative or even competitive, improving standard organic methods. The most recent achievements of the last five years will be covered here, presenting only the most impressive results.

Non-covalent interactions between anions and a cationic rhenium diamine complex: structural characterization of the supramolecular adducts

The behavior of the new cationic complex [Re(CNtBu)(CO)3(N–N)]+ (N–N = 1,2-phenylenediamine) toward several inorganic anions (X−) has been investigated both in solution (by 1H NMR) and in the solid state (by X-ray diffraction), and the results show the formation of supramolecular adducts featuring N–H⋯X hydrogen bonds.