Catalytic Syntheses of Polycyclic Compounds Based on Norbornadiene in the Presence of Nickel Complexes: IV. Problems of Regioselectivity in Norbornadiene Codimerization with Activated Olefins

Cyclocodimerization of norbornadiene with acrylates in the presence of bis(³-allyl)nickel is studied. The regio- and stereoselectivities of cycloaddition depend on the catalyst composition, temperature, reactant ratio, and the nature of acrylate. Conditions excluding the side direction (norbornadiene homodimerization) are selected. A mechanism that explains the main regularities of codimerization is proposed.     

Paramagnetic complexes of nickel(I) stabilized by norbornadiene

Nickel(I) compounds whose concentration was 10^–4–10^–6 of the total concentration of nickel added to the system were identified by EPR in the reaction of 2,5-norbornadiene with nickel homoligand allyl complexes Niall₂ (all is C₃H₅, 1-CH₃C₃H₄, or 2-CH₃C₃H₄). The Ni(I) complexes were stable at room temperature under oxygen-free conditions. It was shown that the paramagnetic complexes were in equilibrium with diamagnetic forms. The temperature dependence of the concentration of the paramagnetic species was determined. The structure of the paramagnetic nickel(I) complexes and the possible routes of their formation are discussed on the basis of the obtained data.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 4, pp. 490–493, July–August, 1990.     

Synthesis of Intrinsically Disordered Fluorinated Peptides for Modular Design of High-Signal 19F MRI Agents

¹⁹F MRI is valuable for in vivo imaging due to the only trace amounts of fluorine in biological systems. Because of the low sensitivity of MRI however, designing new fluorochemicals remains a significant challenge for achieving sufficient ¹⁹F signal. Here, we describe a new class of high-signal, water-soluble fluorochemicals as ¹⁹F MRI imaging agents. A polyamide backbone is used for tuning the proteolytic stability to avoid retention within the body, which is a limitation of current state-of-the-art perfluorochemicals. We show that unstructured peptides containing alternating N-ϵ-trifluoroacetyllysine and lysine provide a degenerate ¹⁹F NMR signal. ¹⁹F MRI phantom images provide sufficient contrast at micromolar concentrations, showing promise for eventual clinical applications. Finally, the degenerate high signal characteristics were retained when conjugated to a large protein, indicating potential for in vivo targeting applications, including molecular imaging and cell tracking.     

Unconventional Allylation of Norbornadiene Catalyzed by Palladium Complexes

A new catalytic system based on palladium complex compounds for the unconventional allylation of norbornadiene with allylic esters of carboxylic acids is developed. The structure of reaction products is determined and the factors affecting their ratio are found. Comparative analysis of the palladium and nickel catalytic systems is performed.     

Role of the paramagnetic nickel(I) complex in the catalytic dimerization of norbornadiene

In a joint investigation of the kinetic laws of the catalytic cyclodimerization of norbornadiene in the presence of bis-³-allyl complexes of nickel by gas chromatography and ESR, a definite correspondance in the change in the concentrations of norbornadiene, its dimers, and the paramagnetic nickel(I) complex was detected. The absence of an ESR signal in model systems, as well as the substantial differences in the relative amounts of Ni(I) when bis-₃ -allyl nickel complexes of different structure were used, suggests that paramagnetic Ni(I) does not participate as one of the intermediates in the catalytic process.M. V. Lomonosov Moscow Institute of Fine Chemical Technology. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 27, No. 4, pp. 513–516, July–August, 1991. Original article submitted October 16, 1989.     

Unusual selective allylation of norbornadiene in the presence of palladium nanoclusters

The reaction of norbornadiene (NBD) with allyl acetate in the presence of the nanocluster Pd₁₄₇phen₃₂O₆₀(OCOBu^t)₃₀ (Pd-147; phen is 1,10-phenanthroline) and PPh₃ in acetonitrile is nonselective and is accompanied by the decomposition of the cluster, affording the same allylation products of NBD as the reaction with Pd₃(OAc)₆ or Pd(dba)₂ (dba is dibenzylideneacetone) combined with PPh₃. In contrast, in the ionic liquid [bmim][BF₄] (bmim is 1-butyl-3-methylimidazolinium), the Pd-147 is not decomposed and the reaction occurs selectively to give methylidene(vinyl)norbornene as the sole product. The data obtained suggest that in an ionic liquid, the reaction under study is catalyzed by the nanocluster Pd-147 rather than by the products of its decomposition.     

Catalytic syntheses of polycyclic compounds based on norbornadiene-2,5 in the presence of nickel complexes: II. cyclic dimerization of norbornadiene-2,5. Kinetics and mechanism of the process

Kinetics of the cyclodimerization of norbornadiene-2,5 (NBD) is studied in the presence of a catalytic system based on bis(η³-allyl)nickel. The forms of the rate laws characterized by different reaction orders with respect to NBD are determined. The influence of temperature and solvent nature on the process is studied. The thermodynamic parameters are determined. The structure of the products is shown to be determined by the structure of intermediates. The mechanism of the process, consisting of the following main steps, is proposed: (1) the formation of Ni(NBD)₂, which is the true catalyst; (2) the reversible addition of NBD to the indicated complex, resulting in the formation of Ni(NBD)₃ and Ni(NBD)₄ η-complexes and accompanied by a change in ligand coordination; (3) the oxidative addition of coordinated NBD molecules to a nickel atom that gives five and six-membered metallacyclic intermediates; and (4) the reductive elimination of nickel from them to form cyclic dimers. The conditions for the selective formation of individual isomers are proposed.     

Unconventional catalytic allylation of 5-norbornene-2,3-dicarboxylic anhydrides: 7-oxa and 7-aza analogues

The catalytic allylation of 7-oxanorbornene, 7-azanorbornene, and bicyclo[2.2.2]octenoic anhydride was performed for the first time. It was found that the structures of allylation products and ratios between them were analogous to those for corresponding carbocyclic derivatives. The presence of a substituent at the double bond of a substrate makes this reaction impossible. Comparative experiments were performed for evaluating the relative reactivity of double bonds in 7-oxanorbornene, 7-azanorbornene, and their carbocyclic analogs.     

Paramagnetic nickel(I) complexes and their role in the catalytic dimerization of norbornadiene

The kinetics of the formation of a paramagnetic nickel(I) complex from bis(η³-allyl)nickel under conditions of catalytic norbornadiene dimerization is reported. It is demonstrated by ESR and GLC that the concentrations of Ni(I), norbornadiene and its pentacyclic dimers change in the same way. It might be inferred from this finding that Ni(I) is involved in the catalytic process as an intermediate. However, experiments on model systems have not confirmed this assumption. At the same time, they have not ruled out the participation of the paramagnetic complex in side catalytic reactions. The presence of Ni(I) in the reaction system is connected with the presence of free norbornadiene there. Hypotheses as to the probable structure and formation mechanism of the paramagnetic Ni(I) are suggested.