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1.
The 2,6-dioxabicyclo[3.2.1]octane unit, 10, present in citreoviridinol (1) has been produced in a stereoselective manner by treatment of the epoxide (8) derived from citreoviral (6), (7), with -toluenesulphonic acid. 相似文献
2.
Reaction of nerol () with thallium(III) perchlorate gave 6-oxabicyclo[3.2.1]octane derivatives () and (), and 6,9-dioxabicyclo[3.3.1]nonane derivatives () as the cyclization products. 相似文献
3.
W. Cocker P.D. Cunningham N.W.A. Geraghty T. Higgins P.J. McArdle 《Tetrahedron letters》1984,25(47):5441-5444
The six-membered ring of an -tricyclo [5.1.0.0.3,5] octane derivative is shown by X-ray crystallography to be almost planar. The precise conformation agrees remarkably well with that obtained for the molecule in solution using lanthanide shift reagents. 相似文献
4.
The carbinol is found to rearrange to the bicyclo (2,2,2) octane derivative in the presence of base; the rearrangement involves a transannular reaction in a ten membered ring resulting from an Oxy-Cope system. 相似文献
5.
(1,5)-(-)-Karahana ether (8,8-dimethyl-2-methylene-6-oxabi-cyclo[ 3.2.1]octane) and (1,5)-(-)-karahana lactone (8,8-dimethyl-2-methylene-6-oxabicyclo [3.2.1]octan-7-one) were synthesized from ()-3-hydroxy-2,2-dimethylcyclo-hexanone. The natural karahana lactone was shown to be almost racemic (. 1.3 % e.e.). 相似文献
6.
Isao Kitagawa Hirotaka Shibuya Hiromichi Fujioka Yoshio Yamamoto Akiharu Kajiwara Kunihiro Kitamura Ayako Miyao Toshio Hakoshima Ken-ichi Tomita 《Tetrahedron letters》1980,21(20):1963-1966
Acid treatment of (IR, 3S,1′S)-1-(1′,2′-Epoxyethyl)-1,2,2-trimethyl-3-acetoxymethyl-cyclopentane ) has been shown to yield three products (, , ), among which and are 1-oxa-bicyclo[3.3.0]octane derivatives formed successive methyl migrations followed by an oxorane ring closure. 相似文献
7.
Thi Thanh-Tâm Nguyên Claude Delseth Jean-Pierre Kintzinger Pierre-Alain Carrupt Pierre Vogel 《Tetrahedron》1980,36(19):2793-2797
Natural-abundance 17O-NMR spectra of 7-oxanorbornane exo-3-oxatricyclo [3.2.1.02.4]octane and their unsaturated derivatives (endo cyclic and exocyclic double bonds) have been measured. Linear correlation laws were observed for of these ethers/corresponding hydrocarbons. The “cyclization shifts” for δo in ethers were not correlated by the “cyclization shifts” for δc of the corresponding hydrocarbons. 相似文献
8.
The hazard and inconvenience of storing and handling concentrated hydrogen peroxide can be avoided by using instead the solid complex which 1,4-diazabicyclo[2.2.2] octane forms with hydrogen peroxide, it reacts with trialkylchlorosilanes to give bis(trialkylsilyl) peroxides in good yield. 相似文献
9.
Treatment of N-phenyl- a well as N-methyl-3-(tri-bar|n-butylstannyl)-propionamide with 2 equiv of bar|n-butyllithium in the presence of 1,4-diazabicyclo[2.2.2]octane at ?78°C in tetrahydrofuran produced the corresponding dilithio derivatives (homoenolate dianions) and respectively. Reaction with various electrophiles (1 equiv) gave the terminally substituted amides in good yields. 相似文献
10.
Whereas triethyl phosphite readily reacts with benzoyl chloride to yield the Michaelis-Arbusov product, diethyl benzoyl phosphonate, 1-methyl-4-phospha-3,5,8-trioxabi)cyclo[2.2.2]octane, , is essentially unreactive, even at a higher temperature. The bicyclic phosphite also reacts slower than the triethyl phosphite In an oxidation with t-butyl hydroperoxide. These results are interpreted in terms of the stereoelectronic effect. 相似文献
11.
Joseph J. Gajewski Charles W. Benner Bruce N. Stahlly Ralph F. Hall Ronald I. Sato 《Tetrahedron》1982,38(6):853-862
cis- and trans - 2,3 - Dimethylenemethylenecyclopropane ( and ) interconvert at 160.0° with a small normal kinetic isotope effect (KIE) when the exo-methylene is deuterated, but the 1,3-shift products, 2-methylethylidenecyclopropane, show a large normal KIE, 1.35 and 1.31, when formed from and , respectively. This data can be interpreted in terms of either parallel reactions or a common trimethylenemethane diradical intermediate formed with a normal KIE of 1.11 and closing to 1,3-shift product with a normal KIE of 1.29 due to the effect of deuterium in the required 90° rotation of the exo-methylene carbon.The kinetics of the thermal 1,3- and 3,3-shifts of cis- and rans-3,4-dimethyl-1,2-dimethylenecyclobutane ( and ) were determined in a flow reactor. The first order rate constants are log kCB (sec?1) = 13.7 ? 42,200/2.3 RT and log kTB (sec?1) = 13.6 ? 41,900/2.3 RT (Ea in kcal/m) which compare favorably to that from the parent hydrocarbon. 1,2-dimethylenecyclobutane, after reasonable correction for dimethyl substitution.Rearrangement of and its bis(dideuteriomethylene) derivative at 230.0° revealed a normal KIE of 1.08. This KIE could be interpreted in terms of either a methylene rotational isotope effect in a concerted reaction or formation of a bisallyl diradical with the expected normal rotational IE on closure to the 1,3-shift product of 1.12 with no IE in the ring opening when the result is corrected for return of the biradical to starting material.The kinetics of intramolecular 2 + 2 cycloaddition of 1,2,8,9-decatetraene were determined in a flow reactor. The first order rate constant is log k(sec?1) = 9.4 ? 30,800/2.3 RT (Ea in kcal/m). These energetics are compared with those of other 2 + 2 cycloadditions. The major product is 3,4-dimethylenecyclooctene () which is also found from the minor product, cis-7,8-dimethylenebicvyclo[4.2.0]octane (), at higher temperatures. The trans isomer, , also gives at about the same rate as . 相似文献
12.
tert-Butyl azidoformate () reacts with the conjugate bases of , , (R1 = R2 = CH3), and (R1 = CH3, R2 = H) to give products [, , , and , respectively] in addition to the expected N-(tert-butoxycarbonyl)indole derivatives. 相似文献
13.
Shoji Ando Haruhiko Aoyagi Michinori Waki Tetsuo Kato Nobuo Izumiya Kouji Okamoto Michio Kondo 《Tetrahedron letters》1982,23(21):2195-2198
Gramicidin S (GS) analogs, (D-Ser(Bzl)4,4′]-GS (), [D-Ser4,4′]-GS (), and [L-Orn(Boc)2,2′,D-Ser4,4′]-GS () were synthesized and showed high antibacterial activity. One residue of D-Ser in was converted asymmetrically to D-Ala via α,β-dehydroalanine. 相似文献
14.
J.L. Breton F. Camps J. Coll L. Eguren J.A. Gavin A.G. Gonzalez X. Martorell C. Miravitlles E. Molins J. Torramilans 《Tetrahedron》1985,41(15):3141-3146
A new heliangolide has been isolated from aerial parts of , and identified as (6,10)(3,3a,4,lla)-3a,5,8,11a--tetrahydro-4-acetoxy-3,6, 1O-trimethyl-2,9 (3, 4) -cyclodeca[b] furandione. The structural elucidation of the new compound, named heliangolidin, was carried out by spectral means (MS, IR, 1H and 13C NMR, and two dimensional 1H-13C chemical shift correlations) and X-ray diffraction analysis. 相似文献
15.
The model tripeptide Boc-Gly-S-Ala-Aib-OMe () and the two monothiated analogues Boc-Gly(1ψ2CSNH)-S-Ala-Aib-OMe () and Boc-Gly-S-Ala(2ψ3 CSNH)-Aib-OMe () were synthesized. Peptide was obtained by thiation of using 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide, Lawesson's Reagent (LR), followed by deprotection of the Boc group and coupling with Boc-Gly-OH. Thiation of with LR regiospecifically transformed the protected tripeptide to the monothiated analogue . X-Ray diffraction analysis showed that the type-III β-turn formed by the reference peptide is preserved in the monothiated analogue ; conversely,the structure of the isomeric tripeptide is partially extended. 相似文献
16.
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
17.
Claudio Fuganti Piero Grasselli Giuseppe Pedrocchi-Fantoni 《Tetrahedron letters》1979,20(26):2453-2454
Feeding experiments with (4) [5-3H;5-14C]-leucine () and with the (4) [5-3H;2-14C]-isomer () show that incorporation into the isoprenylated tryptophan derivative echinuline (), produced by , involves, to a large extent, loss of the fragment enbodying the carbon atom at position 2 of the fed amino acid. 相似文献
18.
The conformational behaviour of the methylenemalonaldehyde fragment of the title compounds is characterized by solvent and temperture dependencies of 1J(O), 3J(HO,CO), 3J(HO,C), 4J(CO,CO) and 4J(CO,C) spin-spin couplings as well some (STO-3G) and semiempirical level Molecular orbital calculations. The conformational behaviour of the couplings is also discussed on the basis of some INDO/FPT calculations. The conformations of the two formyls are strongly correlated, the - arrangements being favored. The conformation of the Z-formyl is determined by the steric interaction with the aromatic nucleus. The conformations of the formyls are sensitive to solvent and substitution on the aryl. Approximate populations and couplings of the sites are derived. There is some evidence about the non-planarity of the methylenmalonaldehyde fragnent. Complex formation with Mg(C104)2 is reported. 相似文献
19.
Using known NMR and structural data of solid silicates the linear correlation = 1.14 - 2014 between the isotropic 29Si NMR chemical shifts (ppm) and the “isotropic” mean bond lengths (nm) has been established. The results of semi-empirical calculations are in good agreement with this equation. 相似文献
20.
L.J. Goad F.-X. Garneau J.-L. Simard J.W. ApSimon M. Girard 《Tetrahedron letters》1985,26(29):3513-3516
- 14α-Methyl-5α-cholest-9(11)-en-3β-ol () and 4α,14α-dimethyl-5α-cholest-9(11)-en-3β-ol () have been isolated from the sea cucumber and characterised by 1H NMR, 13C NMR and mass spectrometry. Lanost-9(11)-en-3β-ol () has also been tentatively identified. The relevance of this series of Δ9(11)-sterols to holothurin biosynthesis is briefly discussed. 相似文献