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[reaction: see text]. Photolysis of 3-(hydroxymethyl)benzophenone (1) in aqueous solution (pH < 3) results in clean formation of 3-formylbenzhydrol (2) at dilute (<10(-4) M) conditions. Evidence suggests that the highly efficient (Phi approximately 0.6) reaction involves a unimolecular mechanism and an overall formal intramolecular photoredox process, which requires electronic communication between the 1,3-positions of the benzene ring, an unprecedented example of the photochemical meta effect. The photoredox reaction was not observed in organic solvents, where only photoreduction of the benzophenone moiety was observed. 相似文献
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Dr. Mukesh Pappoppula Dr. Kathryn L. Olsen Devin R. Ketelboeter Prof. Aaron Aponick 《Angewandte Chemie (International ed. in English)》2023,62(48):e202312967
A copper-catalyzed dearomative alkynylation of pyridines is reported with excellent regio- and enantioselectivities. The synthetically valuable enantioenriched 2-alkynyl-1,2-dihydropyridine products afforded are generated from the readily available feedstock, pyridine, and commercially available terminal alkynes. The three-component reaction between a pyridine, a terminal alkyne, and methyl chloroformate employs copper chloride and StackPhos, a chiral biaryl P,N- ligand, as the catalytic system. Under mild reaction conditions, the desired 1,2-addition products are delivered in up to 99 % yield with regioselectivity ratios up to 25 : 1 and enantioselectivities values of up to 99 % ee. Activated and non-activated terminal alkynes containing a wide range of functional groups are well tolerated. Even acetylene gas delivered mono-alkynylated products in high yield and ee. Application of the methodology in an efficient enantioselective synthesis of the chiral piperidine indolizidine, coniceine, is reported. 相似文献
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Kjaergaard HG Garden AL Chaban GM Gerber RB Matthews DA Stanton JF 《The journal of physical chemistry. A》2008,112(18):4324-4335
We have calculated frequencies and intensities of fundamental and overtone vibrational transitions in water and water dimer with use of different vibrational methods. We have compared results obtained with correlation-corrected vibrational self-consistent-field theory and vibrational second-order perturbation theory both using normal modes and finally with a harmonically coupled anharmonic oscillator local mode model including OH-stretching and HOH-bending local modes. The coupled cluster with singles, doubles, and perturbative triples ab initio method with augmented correlation-consistent triple-zeta Dunning and atomic natural orbital basis sets has been used to obtain the necessary potential energy and dipole moment surfaces. We identify the strengths and weaknesses of these different vibrational approaches and compare our results to the available experimental results. 相似文献
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We show that a linear molecule subjected to a short specific elliptically polarized laser field yields post-pulse revivals exhibiting alignment alternatively located along the orthogonal axis and the major axis of the ellipse. The effect is experimentally demonstrated by measuring the optical Kerr effect along two different axes. The conditions ensuring an optimal field-free alternation of high alignments along both directions are derived. 相似文献
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Christian W. Bauer Zoltan Ligeti Martin Schmaltz Jesse Thaler Devin G.E. Walker 《Physics letters. [Part B]》2010
We investigate which new physics signatures could be discovered in the first year of the LHC, beyond the expected sensitivity of the Tevatron data by the end of 2010. We construct “supermodels”, for which the LHC sensitivity even with only 10 pb−1 useful luminosity is greater than that of the Tevatron with 10 fb−1. The simplest supermodels involve s -channel resonances in the quark–antiquark and especially in the quark–quark channels. We concentrate on easily visible final states with small standard model backgrounds, and find that there are simple searches, besides those for Z′ states, which could discover new physics in early LHC data. Many of these are well-suited to test searches for “more conventional” models, often discussed for multi-fb−1 data sets. 相似文献
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