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41.
As part of a programme directed towards the synthesis of the marine toxins, the spirolides and gymnodimine, a convenient synthesis of the key bicyclic spiroimine ring systems has been developed. The method involves double alkylation of a simple lactam, Grubbs ring closing metathesis of the resultant dialkylated lactam then reduction of the lactam to an imine. 相似文献
42.
The complexes Ru(L1-CH3)(CO)3Cl, RuL2(CO)2Cl2, and RuL3(CO)2Cl2 (L1= 6-methoxy-5,8-quinolinedione, L2 = 7-amino-6-methoxy-5,8-quinolinedione, L3 = 6,6'-dimethoxycarbonyl-2,2'-bipyridine) were prepared by reaction of L1-L3 with the tricarbonyldichlororuthenium(II) dimer. L1-L3 act as bidentates through the ortho oxygen atoms, the pyridyl nitrogen and the adjacent quinone oxygen, and the bipyridyl nitrogens, respectively. RuL3(CO)2Cl2 is characterized by X-ray crystallography. 15N NMR correlation spectra give upfield shifts of around 60 ppm for the pyridyl nitrogens that are coordinated to the metal, while 13C NMR correlation spectra give a downfield shift of 10 ppm for the quinone carbonyl group that is coordinated to the metal. The electrochemistry of RuL2(CO)2Cl2 is examined, and the implications for the formation of metal complexes of the antitumor antibiotic streptonigrin, which cleaves DNA in the presence of metal ions, are discussed. 相似文献
43.
44.
This paper reports on studies on the reaction of InCl with SnCl2 to form ternary halides. The reaction route is investigated by x‐ray investigations at different temperatures. Depending on the modification of InCl as educt and on the temperature conditions the reaction follows different pathways which may include intermediate redox reactions of the type In+ + Sn2+ → In3+ + Sn0. 相似文献
45.
A series of enantiomerically pure 8-oxabicyclo[3.2.1]oct-6-en-3-ones functionalized in the unsaturated two-carbon bridge has been prepared by the title reaction. Carbocation reactivity has been fined-tuned at -95 degrees C and adjusted to diene nucleophilicity. Conventional electrophilic substitution of 3-silylated and 3-stannylated furan is suppressed in favor of the rapid 4 + 3 cycloaddition mode. In the case of cycloadduct 13A, stereoselectivity (17:1) is perfectly matched to regioselectivity (17:1). High stereoselection as well as unprecedented regioselection and chemoselection is attributed to the low-temperature cycloaddition protocol and the design of chiral auxiliary and tether. 相似文献
46.
47.
Pentacarbonyl-rhenate and -manganate react with the cationic complexes [cpMo(CO)2(diene)]+, [cpMo(CO)2(cyclopentadiene]+, [cpMo(CO)2(cyclohexadiene)]+, [cpMo(CO)2(trimethylenemethane]+, [(OC)3Mo(η7-C7H7)]+, [cp(OC)-(Ph3P)Mo(alkyne)]+ to give the corresponding heteronuclear hydrocarbon-bridged complexes. 相似文献
48.
Fluorescence-dip infrared spectroscopy and predissociation dynamics of OH A 2Sigma+ (v = 4) radicals
Derro EL Pollack IB Dempsey LP Greenslade ME Lei Y Radenović DC Lester MI 《The Journal of chemical physics》2005,122(24):244313
Fluorescence-dip infrared spectroscopy, an UV-IR double-resonance technique, is employed to characterize the line positions, linewidths, and corresponding lifetimes of highly predissociative rovibrational levels of the excited A (2)Sigma(+) electronic state of the OH radical. Various lines of the 4 <--2 overtone transition in the excited A (2)Sigma(+) state are observed, from which the rotational, centrifugal distortion, and spin-rotation constants for the A (2)Sigma(+) (v = 4) state are determined, along with the vibrational frequency for the overtone transition. Homogeneous linewidths of 0.23-0.31 cm(-1) full width at half maximum are extracted from the line profiles, demonstrating that the N = 0 to 7 rotational levels of the OH A (2)Sigma(+) (v = 4) state undergo rapid predissociation with lifetimes of < or =23 ps. The experimental linewidths are in near quantitative agreement with first-principles theoretical predictions. 相似文献
49.
Transition Metal Complexes with Anions of 1-substituted Tetrazolinones and -thiones and of 1,3-Thiazolin-2-thione The preparation of a series of anionic and phosphine containing complexes with the ambivalent anions of 1-R-tetrazolin-5-ones and -5-thiones, and of 1,3-thiazolin-2-thione is reported. According to the i.r. and 1H n.m.r. spectra the S-heterocycles are bonded through the exocyclic sulfur atom to the metal; in the oxotetrazolinate compounds coordination occurs via the N2 or N4 ring atoms. The copper and silver complexes [(Ph3P)MX]2 (X = anionic heterocycle) have been found to be dimeric. 相似文献
50.
The cover picture shows a model of the "progenitor-TADDOLs" in front of a panorama of the Fünffingersstocks and the Wenden Glacier in the Titlisgebiet (Switzerland). The model is flanked by a stylized view of the general mechanistic model for the preferred stereochemical pathway of the Ti-TADDOLate-catalyzed reaction of chelating substrates (left) and a blackboard (right) showing formulae of compounds that can be prepared with high enantioselectivity by nucleophilic addition in the presence of titanium TADDOLates. From TADDOL, introduced in 1982, a genuine auxiliary system for the "introduction of chirality" (not only by reaction) has been developed, which, in the final sprint against the competition has a good chance of securing a place on the winning podium. The photograph of the mountain landscape was taken by Dr. J. Frackenpohl, the cover picture was generated by one of the authors (A.H.) of the comprehensive review of TADDOLs in this issue (p. 92 ff.) with the help of the program Povray. Supporting information for this article is available on the WWW under http://www.angewandte.com or from the author. 相似文献