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41.
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Anthony J. Burke Elisabete da Palma Carreiro Nuno M.M. Moura Ana Isabel Rodrigues 《Journal of organometallic chemistry》2007,692(22):4863-4874
In our quest to find new ligands for highly stereoselective reactions, we tested a variety of chiral non-racemic pseudo-C2 symmetric bis-oxazolines derived from malonic acid containing an arylidene bridge unit (and appropriately termed Arylid-Box) in the catalytic asymmetric cyclopropanation (CAP) reaction of styrene and ethyl diazoacetate using between only 1-2 mol% of a Cu(I) pre-catalyst. Some very good e.e.s (up to 86%), were obtained. It was possible to isolate 10a′-[Cu(CH3CN)4]PF6 which existed as a bench stable solid that proved to be more efficient than the catalyst prepared in situ. Cu(I) pre-catalysts were used for the first time in the CAP reaction with the Isbut-Box ligands 13a and 13b and, although, the e.e.s were better for ligand 13a using these pre-catalysts, in the case of ligand 11b this was not the case. Spectroscopic studies (UV-Vis and 1H NMR) were carried out to gain an insight into the nature of the catalytic species at work so that the conditions could be optimised giving better results. Some theoretical studies were conducted to try to explain the better enantioselectivities obtained using Evans’ tert-Box-Cu(I) complex over our complex. 相似文献
43.
Polymer films containing dispersions of liquid crystal microdroplets have considerable potential for use in displays and other light control devices. These polymer-dispersed liquid crystal (PDLC) films operate by electric field control of light scattering, rather than by polarization control as in the case of twisted nematic systems. The scattering characteristics of the PDLC films are determined by the refractive indices of the polymer and liquid crystal and by the size of the microdroplets. We have found that it is possible to regulate the microdroplet size by controlling the droplet formation rate (i.e. the cure kinetics of the film). Using calorimetry and scanning electron microscopy, we determined the influence of cure kinetics on microdroplet size for epoxy-based PDLCs. We found that droplet size increased with increasing cure time constant. However, the relationship changed as cure temperature was varied, perhaps as a result of competing cure processes. We also determined the phase behaviour of the epoxy-based PDLCs. The liquid crystal acted as a plasticizer, depressing the glass transition temperature of the PDLC samples slightly below that of the pure epoxy. The temperature and enthalpy of the nematic to isotropic transition of the liquid crystal material in the microdroplets were both functions of cure temperature. From the transition enthalpy it was possible to estimate a, the fraction of liquid crystal contained in the droplets; we found that a decreased with increasing cure temperature, presumably as a result of greater liquid crystal solubility in the epoxy matrix at higher temperatures. 相似文献
44.
The skeletal rearrangement of bicyclo[2.2.2]lactones, involving a mild and chemoselective palladium-catalysed translocation key-step, provides an efficient and diastereoselective access to synthetically useful bicyclo[3.3.0]lactones. 相似文献
45.
We describe the Williams zeta-functions and the twist zeta-functions of sub-Lorenz templates generated by renormalizable Lorenz maps, in terms of the corresponding zeta-functions of the sub-Lorenz templates generated by the renormalized map and by the map that determines the renormalization type. 相似文献
46.
Aillaud I Bossharth E Conreaux D Desbordes P Monteiro N Balme G 《Organic letters》2006,8(6):1113-1116
[reaction: see text] N-Methyl-4-alkoxy-3-alkynylpyridin-2(1H)-ones readily undergo iodine-promoted 5-endo-heteroannulation under mild conditions to 3-iodofuropyridinium triiodide salts in moderate to good yields. The latter may be dealkylated in situ upon exposure to an iodide anion to provide the corresponding 3-iodofuro[2,3-b]pyridin-4(1H)-ones. The same strategy applies to the formation of furo[2,3-b]quinolin-4(9H)-ones. 相似文献
47.
[reaction: see text] Ortho-lithiation of (2R,4S,5R)-3,4-dimethyl-2-ferrocenyl-5-phenyl[1,3,2]oxazaphospholidine 2-oxide 2 was carried out with diastereoselectivity of >99%, affording a new and efficient way for introducing planar chirality into the ferrocene backbone. Various electrophiles were used to quench the lithiated species, showing the wide applicability of the new ortho-directing group and its potential to generate ligands for use in asymmetric catalysis. 相似文献
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Daniel Kaiser Veronica Tona Carlos R. Gonalves Saad Shaaban Alberto Oppedisano Nuno Maulide 《Angewandte Chemie (International ed. in English)》2019,58(41):14639-14643
In comparison to the extensively studied metal‐catalyzed hydroamination reaction, hydroaminomethylation has received significantly less attention despite its considerable potential to streamline amine synthesis. State‐of‐the‐art protocols for hydroaminomethylation of alkenes rely largely on transition‐metal catalysis, enabling this transformation only under highly designed and controlled conditions. Here we report a broadly applicable, acid‐mediated approach to the hydroaminomethylation of unactivated alkenes and alkynes. This methodology employs cheap, readily available, and bench‐stable reactants and affords the desired amines with excellent functional group tolerance and impeccable regioselectivity. The broad scope of this transformation, as well as mechanistic investigations and in situ domino functionalization reactions are reported. 相似文献