Center for Magnetic Resonance

V.A. Rassadin, A.A. Yakimanskiy, E.V. Eliseenkov, V.P. Boyarskiy
“Synthesis of acyclic diaminocarbene palladium complex featuring triethoxysilane moiety”

Inorg. Chem. Comm., 2015, 2015, 61, 21-23
DOI:10.1016/j.inoche.2015.08.008

The first example of an acyclic diaminocarbene palladium complex, viz. cis-[PdCl₂(CN(2,6-Me₂C₆H₃)){C(NH(2,6-Me₂C₆H₃)) = NH(CH₂)₃Si(OEt)₃}], featuring the triethoxysilane moiety is described. The complex was generated from bis(o-xylylisocyanide)palladium dichloride and (3-aminopropyl)triethoxysilane under mild conditions and isolated in 88% yield. The target compound is stable at RT either in the solid state or in CDCl₃ or CD₃OD solutions within several months.

D.S. Bolotin, M.Ya. Demakova, A.S. Novikov, M.S. Avdontceva, M.L. Kuznetsov, N.A. Bokach, V.Yu. Kukushkin
“Bifunctional Reactivity of Amidoximes Observed upon Nucleophilic Addition to Metal-Activated Nitriles”

Inorg. Chem., 2015, 54, 4039-4046
DOI:10.1021/acs.inorgchem.5b00253

Treatment of the aromatic nitrile complexes trans-[PtCl₂(RC₆H₄CN)₂] with the aryl amidoximes p-R′C₆H₄C(NH₂)═NOH, followed by addition of 1 equiv of AgOTf and then 5 equiv of Et₃N, leads to the chelates [PtCl{HN═C(RC₆H₄)ON═C(C₆H₄R′-p)NC(RC₆H₄)═NH}] (15 examples; yields 71−88% after column chromatography) derived from the platinum(II)-mediated coupling between metal-activated nitriles and amidoximes. The combined experimental and theoretical results indicate that the coupling with the nitrile ligands involves both the HON and monodeprotonated NH₂ groups of the amidoximes.

V.A. Rassadin, V.P. Boyarskiy, V.Yu. Kukushkin
“Facile Gold-Catalyzed Heterocyclization of Terminal Alkynes and Cyanamides Leading to Substituted 2-Amino-1,3-Oxazoles”

Org. Lett., 2015, 17, 3502-3505
DOI:10.1021/acs.orglett.5b01592

Facile gold-catalyzed heterocyclization based upon intermolecular trapping of the generated α-oxo gold carbenes with various cyanamides R²R³NCN (R²/R³ = Alk/Alk, −(CH₂)₂O(CH₂)₂–, Ar/Ar, Ar/H) has been developed. In most cases, 2-amino-1,3-oxazoles functionalized at the nitrogen atom as well as at the fifth position of the heterocyclic ring (12 examples) were isolated in good to moderate yields.