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51.
Rolf Hirsenkorn 《Tetrahedron letters》1990,31(52):7591-7594
A new strategy for the asymmetric synthesis of 1-benzyl-1,2,3,4-tetrahydroisoquinolines7 − 9 has been developed. The route involves introduction of asymmetry via enantioselective epoxidation or dihydroxylafion of corresponding stilbene precursors followed by aminolysis and Pomeranz-Fritsch cyclization. The strategy has been successfully applied to the asymmetric synthesis of (R)-reticuline (9), the key-intermediate in the synthesis of morphine alkaloids on the biomimetic route. 相似文献
52.
Adenosine 5'-triphosphate (ATP(4-)) and related nucleoside 5'-triphosphates (NTP(4-)) serve as substrates in the form of metal ion complexes in enzymic reactions taking part thus in central metabolic processes. With this in mind, the coordination chemistry of NTPs is critically reviewed and the conditions are defined for studies aiming to describe the properties of monomeric complexes because at higher concentrations (>1 mM) self-stacking may take place. The metal ion (M(2+)) complexes of purine-NTPs are more stable than those of pyrimidine-NTPs; this stability enhancement is attributed, in accord with NMR studies, to macrochelate formation of the phosphate-coordinated M(2+) with N7 of the purine residue and the formation degrees of the resulting isomeric complexes are listed. Furthermore, the formation of mixed-ligand complexes (including also those with buffer molecules), the effect of a reduced solvent polarity on complex stability and structure (giving rise to selectivity), the use of nucleotide analogues as antiviral agents, and the effect of metal ions on group transfer reactions are summarized. 相似文献
53.
Vitamin-B12-Catalyzed C, C-Bond Formation: Synthesis of Jasmonates via Sequential Radical Reaction The Cbl-catalyzed electroreduction of 3-(2′-bromo-1′-ethoxyethoxy)cyclopenten ( 1a ) in presence of 1-cyanovinyl-acetate ( 8 ) gave, in a sequential radical reaction (5-exo-trig-cyclization of 1a followed by addition to 8 ), 1-cyano-2-(2′-ethoxy-hexahydro-2′H-cyclopenta[b] furan-4′-yl)ethyl acetate ( 10a ). This intermediate was transformed to methyl jasmonate ( 7 ; four steps) and epituberolide ( 9 ; three steps) in 20 and 31% yield, respectively, from cyclopent-2-en-l-ol. 相似文献
54.
Edgar Heilbronner Rolf Gleiter Toshihiko Hoshi Armin de Meijere 《Helvetica chimica acta》1973,56(5):1594-1604
To obtain further information concerning the interaction between Walsh-orbitols of ‘conjugated’ cyclopropane rings, the photoelectron spectra of the following compounds have been recorded: bicyclo[4.1.0]heptane 1 , cis- and trans-tricyclo[5.1.03, 5]octane 2, 3 , diademane 4 , trans-pentacyclo[3.3.2.02, 9.04, 10, 06, 8]decan 5 and bicyclo[4.1.0]heptene-2 6 . The first bands in the PE.-spectra of these compounds have been assigned on the basis of a ZDO HMO-approximation. For 2 and 4 the value for resonance integral between linked 2p atomic orbitals of two adjacent eclipsed cyclopropane rings is found to be ?1.73 eV. 相似文献
55.
Contrary to the informations in the literature our results of equilibrium and kinetic measurements indicate that Al(III) and Pyridine-2,6-dicarboxylic Acid in the range ofpH=(3...5) only formed the complexes AlHL
2+ (log=7.44±0.2) and AlL
+ (log=11.37±0.06). 相似文献
56.
S. P. Singh S. S. Parmar V. I. Stenberg S. A. Farnum 《Journal of heterocyclic chemistry》1978,15(1):13-16
The 13C nmr chemical shifts of phenylbutazone, oxyphenbutazone, indomethacin and indole-3-acetic acid are reported. The assignments of various carbon resonances are made on the basis of the substitution effects on benzene shifts, multiplicities generated in SFORD spectra, nuclear overhauser enhancement for protonated carbons, and the comparison with analogous compounds. 相似文献
57.
Virgil I. Stenberg Nand K. Narain S. P. Singh Ralph H. Obenauf M. J. Albright 《Journal of heterocyclic chemistry》1977,14(3):407-410
The 15N and 13C nmr spectra of physostigmine are discussed along with complete assignment of the signals. This alkaloid 15 N nmr spectrum is notable because it contains nitrogens in three different environments. 相似文献
58.
59.
Rolf Niedermayer 《Angewandte Chemie (International ed. in English)》1975,14(4):212-218
Synthesis of organometallic materials can be accomplished in many cases by cocondensation of metal atoms and organic molecules at low temperatures. The reaction kinetics is determined by the competition between metal cluster growth and formation of the organometallic compound. Interesting compounds may contain one or more metal atoms; the latter type could be obtained by reaction between a cluster containing the desired number of metal atoms and an organic molecule. A precise knowledge of the events occurring on condensation of metal atoms and cluster formation can therefore be of value in the control of chemical synthesis. These phenomena have been investigated in connection with the study of the growth of thin metallic films, both experimentally and theoretically. Direct observation of the formation of very small clusters is difficult. The good agreement between experimental results and recent calculations for the development of large clusters, however, allows reliable theoretical conclusions for the first stages of adsorption and cluster formation. The present contribution describes experimental work on film growth and relevant theoretical concepts, and an attempt is made to develop applications to organometallic synthesis. 相似文献
60.
Sánchez-Moreno MJ Gómez-Coca RB Fernández-Botello A Ochocki J Kotynski A Griesser R Sigel H 《Organic & biomolecular chemistry》2003,1(10):1819-1826
The synthesis of (1H-benzimidazol-2-yl-methyl)phosphonic acid, H2(Bimp)+/-, is described: 2-chloromethylbenzimidazole was reacted with ethylchloroformate to give 1-carboethoxy-2-chloromethylbenzimidazole which was treated with trimethyl phosphite and after hydrolysis with aqueous HBr H2(Bimp)+/- was obtained. In H2(Bimp)+/- one proton is at the N-3 site and the other at the phosphonate group; both acidity constants were determined in aqueous solution by potentiometric pH titrations (25 degrees C; I = 0.1 M, NaNO3) and this furnished the pKa values of 5.37 +/- 0.02 and 7.41 +/- 0.02, respectively. The acidity constant for the release of the primary proton from the P(O)(OH)2 group of H3(Bimp)+ was estimated: pKa = 1.5 +/- 0.2. Moreover, Bimp2- can be further deprotonated at its neutral (N-1/N-3)H site to give the benzimidazolate residue, but this reaction occurs only in strongly alkaline solution (KOH); application of the H_ scale developed by G. Yagil (J. Phys. Chem., 1967, 71, 1034) together with UV spectrophotometric measurements gave pKa = 14.65 +/- 0.12. Comparisons with acidity constants taken from the literature show that this latter pKa value is far too large and this allows the conclusion that an intramolecular hydrogen bond is formed between the (N-1/N-3)H site and the phosphonate group of Bimp2-; the formation degree of this hydrogen-bonded isomer is estimated to be 98 +/- 2%. The general relevance of this and the other results are shortly discussed and the species distribution for the Bimp system in dependence on pH is provided. 相似文献