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1.
Various β-dicarbonyl compounds can be hydroxylated as their silyl enol ethers by -chloroperbenzoic acid (MCPBA). 相似文献
2.
A reinvestigation of the stereoselectivities for the epoxidation of acyclic allylic alcohols with MCPBA, and with -butyl hydroperoxide catalyzed by V+5 and Mo+6 revealed a number of errors in our original work1 which are rectified. Optimum O-C-C=C dihedral angles are proposed. 相似文献
3.
Low temperature 1H NMR and 13C NMR, and IR suggest that the -chloroperbenzoic acid (MCPBA) oxidation of neopentyl neopentanethiolsulfinate leads to the formation of (E)- and (Z)-2,2-dimethylpropanethial S-oxide, neopentyl neopentanethiolsulfonate, and other products. 相似文献
4.
In contrast with the reaction of α-aminonitriles a, the corresponding -acylated α-aminonitriles b-f and oxalyl chloride do not yield pyrazinone derivatives, but 5-aminooxazoles - or 4(5)-imidazolones , the latter being converted in some cases into imidazo [2,1-]isoquinoline-2,5,6(3)-triones. Reactions of compounds b-f and ethyl chlorooxoacetate provide evidence for a 5(4)-iminooxazole intermediate , which aromatizes to yield 5-aminooxazoles -; however, unaromatizable īntermediates of type - isolable as 5(4)y-oxazolones after hydrolysis - undergo a catalyzed Dimroth-type rearrangement to give imidazolone derivatives . 相似文献
5.
Nancy W. Withers W.C.M.C. Kokke Michel Rohmer W.H. Fenical Carl Djerassi 《Tetrahedron letters》1979,20(38):3605-3608
The sterol fraction of the cultured dinoflagellate contains in addition to cholesterol, 24-methylcholesterol, 4,24-dimethylcholesterol and dinosterol () small amounts of the cyclopropyl-containing sterols gorgosterol () and 5α-gorgostanol () as well as 4α-methylgorgostanol () and E-4α,22ξ,23ξ (or 24ξ)-trimethylcholest-17(20)-en-3β-ol ( or ). The biosynthetic implications of the first isolation of such sterols from a free-living alga are emphasized. 相似文献
6.
General methods for inverting the stereochemisty of vinyl -alcohols such as and into and respectively are described. The procedures employ a [2,3] sulfoxide rearrangement and will facilitate the extended use of the oxy-Cope rearrangement to a variety of related ring systems. 相似文献
7.
A new synthesis of (±), (+)- and (-)-lineatin (3,3,7-trimethyl-2, 9-dioxatricyclo [3.3.1.04,7] nonane, ) was achieved. The stereochemistry of (+)-lineatin was established as 1, 4, 5, 7 by an X-ray crystallographic analysis of an intermediate . 相似文献
8.
W.David Ollis Julia Stephanidou Stephanatou J.Fraser Stoddart Gulten G. Unal David J. Williams 《Tetrahedron letters》1981,22(23):2225-2228
An X-ray structure analysis shows that the 5, 18-dimethyl derivative () of the title compound () crystallises from xylene as a 1:1 inclusion compound in which the host molecules adopt propeller-like conformations ( and *) with almost perfect 2 symmetry. Dynamic 1H n.m.r. spectroscopy shows that the 5, 18-dibenzyl derivative () of () forms a 1:1 inclusion compound with ethanol in the solid state and undergoes ring inversion ( ? *) between enantiomeric propeller-like conformations in solution against a barrier of 21.1 kcal mol?1 相似文献
9.
A tritriacontanucleotide which has the sequence of the 5half molecule of E.coli glycine tRNA2, was synthesized by the phosphotriester method involving p-anisidate protection for the 3phosphate ends. Di- and trinucleotide units were prepared from 5dimethoxytrityl-2O-tetrahydrofuranyl-3?-O-(o-chlorophenyl)phosphoryl derivatives of uridine, N-benzoylcytidine, N-benzolyadenosine and N-iso-butyrylguanosine by condensation with 35unprotected nucleosides followed by phosphorylation to give 3phosphodiester blocks. The 3terminal dimers and trimers were synthesized by using 3(o- chlorophenyl)phosphoro-p-anisidates instead of 3?,5?-unprotected nucleosides. The 3?-phosphodiesters of oligonucleotides with a chain length of larger than 5 were obtained by removal of the 3?-phosphoro-p-anisidate with isoamyl nitrite. The 5dimethoxytrityl group was removed by treatment with zinc bromide under anhydrous conditions. Fragments were designed to use common dimer blocks and to reduce the step for 5deblocking of larger fragments. Finally a 3phosphodiester block with a chain length of 20 was condensed with a 5OH component (tridecanucleotide). The fully protected 33 mer was deblocked and purified by chromatography. The structural integrity of the product was confirmed by mobility shift analysis and complete digestion with RNase T2. 相似文献
10.
Felix H. Cano Concha Foces-Foces Manuel Bernabe Jesus Jimenez-Barbero Manuel Martin-Lomas Soledad Penades-Ullate 《Tetrahedron》1985,41(18):3875-3886
X-Ray and 1H N.M.R. studies on pyranoid rings 1,2--fused to dioxolane rings in acetylated -gluco- and --galactopyranose derivatives demonstrate that the configuration of the dioxolane ring influences the conformation of the pyranoid ring in the -gluco but not in the -galactopyranose series. The crystal structure of 3,4,6-tri--acetyl-1,2--(R)--(l-cyano-ethylidene)-α--glucopyranose () and 3,4,6-tri--acetyl-1,2--()-(1-cyano-ethylidene)-α--galactopyranose ()have been determined by X-ray analysis. Lattice parameters for are a=20.6021 (11), b=8.0438 (2), c=5.5541 (1) Å and β= 95.588 (3)° for a cell with P21 symmetry. These parameters for are a=20.3361 (7), b=10.0907 (2), c=18.9115 (5) Å, β =112.399 (2)°, C2, with two crystallographycally independent molecules. The conformation of the pyranoid ring in both compounds can be described as flattened 4C1 and that of the dioxolane ring as distorted E1. The importance of the torsion angles for describing problems of configuration is remarked and the use of relative configurational angles is stressed. The 1H N.M.R. spectra of and and 3,4,6-tri--acetyl-1,2-O-(S)- and (R)-ethylidene-α--glucopyranose ( and ), 3,4,6-tri-O-acetyl--1,2-O-(S)- and ()-ethylidene-α--galactopyranose ( and ), and 3,4,6-tri--acetyl-1,2--()-and ()-benzylidene-α--glucopyranose ( and ) have been analyzed by using iterative computer methods and N.O.E. measurements. The results indicate that the major solution conformation of the pyranoid ring of the derivatives in the -gluco series , and may be described as flattened 4C1 and that of and as 25. The major solution conformation of the pyranoid ring in all compounds in the -galacto series (,,,) may be described as flattened 41. 相似文献
11.
Di--alkylamines can be synthesized efficiently by a three-step process: (1) oxidation of a -alkylamine to a -alkylnitroso compound with peracetic acid in ethyl acetate (2) conversion of the -alkylnitroso compound to a tri--alkylhydroxylamine by successive trapping of two -butyl radicals and (3) sodium naphthalide reduction to the di--alkylamine. 相似文献
12.
Ronald J. Quiann Richard P. Gregson Alan F. Cook Robert T. Bartlett 《Tetrahedron letters》1980,21(6):567-568
A new pharmacologically active agent isolated from the marine sponge has been identified as 1-methylisoguanosine () by spectral and degradative chemical methods and synthesis from a β-D-ribofuranosylimidazole (). 相似文献
13.
Although the hydrochloride of -4--butyl-1-phenyl--1-(N-piperidyl)cyclohexane crystallizes in the conformation with axial -butyl, it exists as an almost equimolar mixture of the two chair conformers in CD2 Cl2 solution. The position of equilibrium allows one to calculate ΔG°-Bu as ?4.9 kcal/mol. 相似文献
14.
A new purine derivative with cytokinin activity was isolated from the cuckoo-pint fruits () and identified as 6-(o-hydroxybenzylamino)-2-methylthio-9-β-D-glucofuranosylpurine . 相似文献
15.
Hideo Kigoshi Yoshikazu Shizuri Haruki Niwa Hiyoyuki Yamada 《Tetrahedron letters》1982,23(14):1475-1476
Isolation and structural elucidation of two new acetylenic polyenes, -laurencenyne and -neolaurencenyne from the marine red alga were carried out, the former compound very recently being proposed to be a biosynthetic precursor of the C15 halogenated cyclic ethers, and . 相似文献
16.
The 1H and 13C nmr spectra of , -9-oxobicyclo[3.3.1]nonane-2,4-dicarboxylic acid, 3, in DMSO-d6 or alkaline D2O, clearly show that it exists in a --conformation with carboxyl groups, thus being the first case of - preference of a bicyclo[3.3.1] nonan-9-one due to the presence of ,-2,4- substituents. 相似文献
17.
Structure of biluciferyl (luciferyl radical dimer), which is produced by chemical oxidation of . luciferin with such as ferricyanide, was determined to be the symmetric 5,5′-dimer of . luciferin. It gives light in the presence of . luciferase, although the bioluminescent rate is very low. We suggest that the biluciferyl is an intermediate in the oxidation of the luciferin to . luciferinol. 相似文献
18.
Makoto Ojika Yoshikazu Shizuri Haruki Niwa Kiyoyuki Yamada Shuichi Iwadare 《Tetrahedron letters》1982,23(47):4977-4980
The structure of reductiline, a metabolite of a variant of was elucidated as () based on chemical and spectroscopic evidence. Transformation of an antitumor antibiotic reductiomycin () into reductiline () was carried out. Synthesis of reductiline () was achieved starting from β-cyanopropionaldehyde dimethylacetal. 相似文献
19.
J Leitich 《Tetrahedron letters》1980,21(32):3025-3028
The relative rates of formation of and [2+2]cycloadducts of benzyne to , - and , -1,5-cyclooctadiene, - and -cyclooctene are discussed and properties of the adducts (e.g., their unusual hydrogenation) are described. 相似文献
20.
The reaction of phenyl lithium acetylide () with 2,6-diphenylpyrylium perchlorate () is solvent dependent. With diethyl ether as solvent, the isolated product differed from that previously reported and is reassingned as 2,6-diphenyl-4-phenylacetylenyl-4-pyran (). On the other hand, in THF the title compound () was obtained; its structure confirmed by single-crystal x-ray crystallography. 相似文献