A mononuclear Dy(III) complex with a non-Schiff base compartmental ligand has been prepared and characterised by X-ray crystallography and ac magnetic susceptibility measurements. The complex exhibits SIM behaviour induced by dilution and/or magnetic field with two thermally activated relaxation processes.
A DFT/B3LYP model study has been carried out on the cyclocarbopalladation and on an unusual 1,5 vinyl to aryl palladium shift which are the two first steps of a cyclocarbopalladation-Stille coupling tandem reaction of various gamma-bromopropargylic-1,2 diols with alkenyls or alkynyl stannanes catalyzed by Pd(PPh(3))(4). From the calculations, the active intermediates in the catalytic process appear to bear a single phosphine ligand, the palladium(II) center keeping in all cases a square-planar coordination pattern either through intramolecular binding of the triple bond or via an intramolecular Pd...C(phenyl) interaction. The computation of the various transition states and intermediates for the 1,5 vinyl to aryl palladium shift reveals that the intimate mechanism of this pathway corresponds to a one-step hydrogen transfer between the two negatively charged carbon atoms of the vinyl and phenyl groups. A two-step pathway involving a Pd(IV) intermediate is not likely to occur. This conclusion may apply to other 1,n-palladium shifts which have been experimentally observed in various organometallic transformations.
Three SHOP-type catalysts, in which the C=C(O) double bond was substituted by electron-withdrawing substituents, [Ni{Ph2PC(R1)=C(R2)O}Ph(PPh3)] (2: R1,R2 = -C(Me)=NN(Ph)-; 3: R1 = CO2Et, R2 = Ph; 4: R1 = CO2Et, R2 = CF3), were assessed as ethylene-oligomerisation and -polymerisation catalysts and compared to Keim's complex, [Ni{Ph2PCH=C(Ph)O}Ph(PPh3)] (1). A rationale for the influence of the double-bond substituents of the P,O-chelate unit on the catalytic properties is proposed, on the basis of X-ray diffraction studies, spectroscopic data and DFT-B3 LYP calculations. Whatever their relative electron-withdrawing strength, the R1 and R2 substituents induce an increase in activity with respect to catalyst 1. For those systems in which the basicity of the oxygen atom is decreased relative to that of the phosphorus atom, the chain-propagation rate increases with respect to that for catalyst 1. Reduction of the basicity of the P relative to that of the O, however, induces higher chain-termination rates.
Nitrogen-containing heteroaromatic cores are ubiquitous building blocks in organic chemistry. Herein, we present a family of metal-free intermolecular formal cycloaddition reactions that enable highly selective and orthogonal access to isoquinolines and pyrimidines at will. Applications of the products are complemented by a density functional theory mechanistic analysis that pinpoints the crucial factors responsible for the selectivity observed, including stoichiometry and the nature of the heteroalkyne.
A mild method for the selective esterification of primary alcohols is described. The use of different phosphines, I(2), and imidazole allows the selective esterification of a wide variety of acids with excellent results. The generation of a bulky phosphonium-carboxylate salt as intermediate could justify the selectivity observed in this process. Additionally, amides also can be synthesized with use of this method.
In the present work, two new copper complexes 3a and 3b with a CuO cubane core are reported. Both complexes are obtained by means of the in situ conversion of the imine functionality of Schiff's base ligands 1a [(E)-4-chloro-2-((thiazol-2-ylimino)methyl)phenol] and 1b [(E)-4-bromo-2-((thiazol-2-ylimino)methyl)phenol] into amino alcohols 2a (4-chloro-2-(hydroxy(thiazol-2-ylamino)methyl)phenol) and 2b (4-bromo-2-(hydroxy(thiazol-2-ylamino)methyl)phenol), respectively. The ligand transformation may be metal assisted and the generated ligands show an interesting mode of coordination in which the alkoxo-O atom binds in a μ-manner connecting simultaneously three copper centers and forming a CuO cubane core. The first analysis of single crystal X-ray diffraction studies reveals that both molecules possess a [4 + 2] cubane-type core, and low temperature magnetic measurements show antiferromagnetic behaviour, in agreement with DFT calculations. However, the best fit and DFT calculations point out three pairs of coupling constants, more coherent with a [2 + 2 + 2] situation, in accordance with the fine analysis of structural data. Finally, phenoxazinone synthase activity has been measured for both molecules, finding k = 86.3 h for the chloride derivative copper(ii) complex in methanol, whereas the bromide derivative copper(ii) complex displays k = 3.4026 × 10 h and 10.289 × 10 h in methanol and DMSO, respectively.
We describe a new strategy to control the number of cyclization steps in bioinspired radical (poly)cyclizations involving epoxypolyenes containing keto units positioned along the polyene chain. This approach provides an unprecedentedly straightforward access to natural terpenoids with pendant unsaturated side chains. Additionally, in the case of bi- and tricyclizations, decalins with cis stereochemistry have been obtained as a consequence of the presence of the ketone. The preferential formation of cis-fused adducts was rationalized using DFT calculations. This result is completely unprecedented in biomimetic cyclizations and permits the access to natural terpenoids with this stereochemistry, as well as to non-natural analogues.
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