A series of five cyanoximes (compounds having the general formula NC-C(=NOH)-R, where R is an amide or carboxylic ester group) have been synthesized and spectroscopically and structurally characterized. These are 2-cyano-2-isonitrosoacetamide (later HACO), 2-cyano-2-isonitrosothioacetamide (HTCO), 2-cyano-2-isonitrosoethylacetate (HECO), 2-cyano-2-isonitroso-N-piperidinylacetamide (HPiPCO), and 2-cyano-2-isonitroso-N-morpholinylacetamide (HMCO). A high yield method of synthesis was developed for the last two previously unknown amidocyanoximes. Variable temperature (13)C NMR studies in DMSO-d(6) solutions allowed the determination of rotational energy barriers for these two new cyanoximes. The HPiPCO and HMCO oxime molecules adopt a trans-anti configuration in the solid state according to X-ray analysis. Reactions between aqueous solutions of K(+)L(-) (L = cyanoximate anions: TCO(-), PiPCO(-), and MCO(-)) and K(2)[MCl(4)] (M = Pd, Pt) resulted in the formation of ML(2) complexes. The crystal structure of Pd(MCO)(2).DMSO was determined and showed the formation of coplanar dimeric [Pd(MCO)](2) units with 3.13 A Pd...Pd separation. The complex adopts cis geometry with anions being in the nitroso form. In the presence of bivalent Pd and Pt, ACO(-) and ECO(-) anions completely or partially hydrolyze in aqueous solutions to the dianion of 2-cyano-2-isonitrosoacetic acid (AACO(2-)). The crystal structure of the product of the hydrolysis reaction, K(2)[Pd(AACO)(2)].4H(2)O, was determined. Data revealed planar and cis geometry of the [Pd(AACO)(2)](2)(-) anion where cyanoximes are in the nitroso form and adopt a cis-anti configuration. All synthesized cyanoxime ligands and nine of their Pd(II) and Pt(II) complexes were tested in vitro on antiproliferating activity using human cervical cancer HeLa cell lines, and cisplatin as a positive control substance. Two out of the nine studied complexes, Pd(MCO)(2) and Pt(MCO), were found to be active compounds inflicting death on 28% and 16% of the cells, respectively, with 55% value for the cisplatin under the same conditions.

Chiral, C2-symmetric imidazolium and imidazolinium ions, as well as the corresponding copper or silver bound carbenoids, have been prepared. Structural study of these compounds by X-ray crystallography reveals a chiral pocket that surrounds the putative carbene site or the metal-carbene bond, at carbon 2, in three of the four ligands prepared. Preliminary investigation into the application of these complexes has shown one of them to be highly enantioselective in the hydrosilylation of acetophenone.

An efficient method for the synthesis of 2-alkyl- and 2-aryl pyrrolidines, piperidines, and azepanes from lactams, in either racemic or enantiopure form, is presented. The lactam nitrogens are acylated with either Boc anhydride or trans-cumylcyclohexyl (TCC) chloroformate. Selective reduction of the lactam carbonyl to the carbinolamide is followed by treatment with benzotriazole. Substitution of the benzotriazole is accomplished by treatment with organometallics, yielding the 2-substituted heterocycles. With TCC, up to 90% diastereoselectivity is achieved. After diastereomer purification, reductive removal of the auxiliary affords enantiopure 2-substituted heterocycles. A mechanistic hypothesis is presented that details the conformational equilibria of the key step.

N-Methyl trans-fused perhydroisoindolines substituted with a tributylstannyl group in the 2-position have been prepared and used as precursors of the corresponding alpha-aminoorganolithiums. The steric course of the reactions of these and other conformationally rigid organolithiums with various electrophiles is summarized and compared with the steric course of the unsubstituted analogs. A mechanistic rationale for the steric course of electrophilic substitutions of these organolithiums is discussed. Pathways involving both polar electrophilic substitutions and radical couplings were observed with different electrophiles.