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521.
Here we report the use of 2-piperidino-1,2,2-triphenylethanol (5) as an outstanding catalyst for the ligand-catalyzed arylation of aldehydes. The use of 5 and a 2/1 mixture of Et(2)Zn/Ph(2)Zn provided the corresponding chiral diarylcarbinols with enantiomeric excess of up to 99% ee. The effect of temperature on the reaction enantioselectivity was studied and the inversion temperature (T(inv)) was determined to be 10 degrees C for reaction with p-tolylaldehyde. Most remarkably, lowering the amount of catalyst (5) to 0.5 mol % still afforded excellent levels of enantiocontrol (93.7% ee). Kinetics of the catalyzed and uncatalyzed arylation of aldehydes was studied by means of in situ FT-IR. The background uncatalyzed addition rates to p-tolylaldehyde when using pure Ph(2)Zn and Et(2)Zn/Ph(2)Zn (2/1) suggest that in the latter case a mixed zinc species forms (EtPhZn) minimizing the undesired nonselective addition. Formation of EtPhZn was modeled at the DFT calculation level. A four-center TS (TS-V) corresponding to the Et/Ph scrambling was localized along with two dimers (D-IV and D-VI). The model supports the hypothesis that Et/Ph exchange is a kinetically facile process. Gas evolution experiments during the formation of the active catalyst showed that the formation of an active site with a ONZn-Et (10) moiety is kinetically favored over ONZn-Ph (11). Finally, the phenyl transfer to benzaldehyde was modeled at the PM3(tm) level through anti and syn 5/4/4 tricyclic TS structures for both 10 and 11. The model could correctly predict the sense and selectivity of the overall process and predicted that 11 should be more selective than 10.  相似文献   
522.
Summary The reaction of [Mo(CO)6] with NOHSO4 gives new [Mo(NO)2(CO)2(HSO4)2], [Mo(NO)3(HSO4)3] and [Mo(NO)4(HSO4)2] (HSO4)2 polynitrosyl molybdenum complexes. The structure of none of the complexes was fully determined. The last is probably a hyponitritonitrosyl complex. [Mo(NO)3(HSO4)3] and [Mo(NO)4(HSO4)2] (HSO4)2 with EtAlCl2 form heterogeneous catalytic systems for olefin metathesis.  相似文献   
523.
A series of tripodal amidopyridine receptors capable of selective recognition of methylmethanetriacetic acid (MMTA) in organic solvents is described. Intramolecular hydrogen-bonding groups, built into some of the receptors, were designed as preorganization devices. Binding was studied by NMR titration, variable temperature NMR experiments, 2D-NMR, isothermal titration calorimetry, and single-crystal X-ray crystallography. The results reveal that a balancing act between inter- and intramolecular hydrogen-bonding interactions in the complexes governs both the dynamics and the geometry of binding. Receptor 1b (without intramolecular hydrogen-bonding groups) features a simple symmetric MMTA binding geometry with optimal enthalpic interactions. In sharp contrast, receptor 1a (with intramolecular hydrogen-bonding groups) reveals a temperature-dependent dual binding mode where MMTA can bind in two completely different geometries. The two solution binding geometries of 1a.MMTA were unraveled by NMR experiments and correlated to the X-ray structures.  相似文献   
524.
The X-ray structures of fifteen 1, 3-imidazolidine, 1, 3-oxazolidine, 1, 3-dioxan-4-one, and hydropyrimidine-4(1H)-one derivatives are described (Table 2) and compared with known structures of similar compounds (Figs. 1–20). The differences between structures containing exocyclic N-acyl groups and those lacking this structural element arise from the A1,3 effect of the amide moieties. Even t-Bu groups are forced into axial positions of six-ring half-chair or into flag-pole positions of six-ring twist-boat conformers by this effect (Figs. 16–20). In the N-acylated five-membered heterocycles, a combination of ring strain and A1, 3 strain leads to strong pyramidalizations of the amide N-atoms (Table 1) such that the acyl groups wind up on one side and the other substituents on the opposite side of the rings (Figs. 4–9 and Scheme 3). Thus, the acyl (protecting!) groups strongly contribute to the steric bias between the two faces of the rings. Observed, at first glance surprizing stereoselectivities of reactions of these heterocycles (Schemes 1 and 2) are interpreted (Scheme 3) as an indirect consequence of the amide A1, 3 strain effect. The conclusions drawn are considered relvant for a better understanding of the ever increasing role which amide groups play in stereoselective syntheses.  相似文献   
525.
Replacement of all phenyl groups in meso-tetraphenylporphyrin, TPP, by [2.2]paracyclophane, PCP, enhances the increase of energy of the HOMO and HOMO-1 of porphine, P, already noticed for the mono-[2.2]paracyclophanyl-substituted TPP, and fills the energy gap by the occupied MOs of the PCP units. The first oxidation half-wave potential is respectively decreased to 0.52 V. The CNDO/S-CIS calculations agree with the experimental bathochromic shifts of all bands in the electronic spectra of the considered atropoisomers of the title compound, TPCPP, as compared to TPP. In the excited B states the interactions between the PCP and porphine units are represented mainly by the charge transfer of 0.44 e from PCP to P, according to transition density matrix calculations. While electroreduction of the title compound results in a successive formation of the anion radical and dianion, oxidation represents a four-step process involving one electron transfer per step, and resulting in the oxidation of two PCP units. Formation of the conductive polymeric film on the electrode seems to be connected with the transient formation of a quinoid system of bonds.  相似文献   
526.
A unique methine moiety attached to three heteroatoms (O, P, S) and contained in the PuPHOS and CamPHOS ligands serves as a strong hydrogen-bond donor. Nonclassical hydrogen bonding of this methine with an amido-carbonyl acceptor provides a completely diastereoselective ligand exchange process between an alkyne dicobalthexacarbonyl complex and a phosphine ligand. This weak contact has been studied by means of X-ray analysis, 1H NMR, and quantum mechanical calculations and revealed that the present interaction falls in the range of strong C-H...O=C bonds. The hydrogen-bond bias obtained in the ligand exchange process has been exploited in the asymmetric intermolecular Pauson-Khand reaction to yield the corresponding cyclization adducts in up to 94% ee.  相似文献   
527.
In nature, coordinated communication between different entities enables a group to accomplish sophisticated functionalities that go beyond those carried out by individual agents. The possibility of programming and developing coordinated communication networks at the nanoscale—based on the exchange of chemical messengers—may open new approaches in biomedical and communication areas. Here, a stimulus-responsive circular model of communication between three nanodevices based on enzyme-functionalized Janus Au–mesoporous silica capped nanoparticles is presented. The output in the community of nanoparticles is only observed after a hierarchically programmed flow of chemical information between the members.

A community of three nanodevices communicates through a hierarchically programmed circular flow of chemical information between members.  相似文献   
528.
A convenient and higher yielding synthetic route to N-alkyl-bis(thiophene)- and N-alkyl-bis(ethylenedioxythiophene) carbazole derivatives is reported and their aggregation, and electrochemical properties are characterized. The key step in the synthesis of this group of compounds has been the Stille-type coupling reaction between the N-alkyldibromocarbazole and tin derivatives of thiophene or ethylenedioxythiophene, as the best way for preparation of conjugated N-alkylcarbazole derivatives. For this group of compounds we also present an electrochemical polymerization effect.  相似文献   
529.
Summary The 3CuCl2·4hmta·2HCl·2H2O complex (hmta=hexamethylenetetramine) has been obtained from acid solution. Spectroscopic and magnetic investigations indicate that, in the crystal structure of this compound, the polymeric chains, 3CuCl2·2hmta·2H2O, and hmta·HCl groups occur.  相似文献   
530.
Two isomeric Ru(II) complexes containing the dinucleating Hbpp (3,5-bis(2-pyridyl)pyrazole) ligand together with Cl and dmso ligands have been prepared and their structural, spectroscopic, electrochemical, photochemical, and catalytic properties studied. The crystal structures of trans,cis-[Ru(II)Cl(2)(Hbpp)(dmso)(2)], 2a, and cis(out),cis-[Ru(II)Cl(2)(Hbpp)(dmso)(2)], 2b, have been solved by means of single-crystal X-ray diffraction analysis showing a distorted octahedral geometry for the metal center where the dmso ligands coordinate through their S atom. 1D and 2D NMR spectroscopy corroborates a similar structure in solution for both isomers. Exposure of either 2a or 2b in acetonitrile solution under UV light produces a substitution of one dmso ligand by a solvent molecule generating the same product namely, cis(out)-[Ru(II)Cl(2)(Hbpp)(MeCN)(dmso)], 4. While the 1 e(-) oxidation of 2b or cis(out),cis-[Ru(II)Cl(2)(bpp)(dmso)(2)](+), 3b, generates a stable product, the same process for 2a or trans,cis-[Ru(II)Cl(2)(bpp)(dmso)(2)](+), 3a, produces the interesting linkage isomerization phenomenon where the dmso ligand switches its bond from Ru-S to Ru-O (K(III)(O)(-->)(S) = 0.25 +/- 0.025, k(III)(O)(-->)(S) = 0.017 s(-1), and k(III)(S)(-->)(O) = 0.065 s(-1); K(II)(O)(-->)(S) = 6.45 x 10(9), k(II)(O)(-->)(S) = 0.132 s(-1), k(II)(S)(-->)(O) = 2.1 x 10(-11) s(-1)). Finally complex 3a presents a relatively high activity as hydrogen transfer catalyst, with regard to its ability to transform acetophenone into 2-phenylethyl alcohol using 2-propanol as the source of hydrogen atoms.  相似文献   
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