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1.
Isoindole or 1H-isoindole, where there is the possibility of tautoinerism, is too unstable to be isolated, and its existence is ascertained only by Diels-Alder addition products with maleic anhydride and N-phenylmaleinimide.1) Moreover, the systematic preparations of isoindole derivatives have not been confirmed.2) However, several successful isoindole syntheses have been realized from ortho-disubstituted benzene derivatives. For instance,3) catalytic reduction over Raney nickel of o-cyanobenzophenone gave 1-phenylisoindole, accompanied by the oxidative coupling product. We wish to report now a synthesis of an isoindole derivative (2) by the dimerization of o-tolunitrile and several reactions of the compound (2), and the physical data were also reported. 相似文献
2.
Trichodiene (1), a sesquiterpene hydrocarbon, was isolated from the extract of mycelium of Trichothecium roseum. The structure of trichodiene (1) was elucidated by Nozoe and Machida in 1970 via degradation and spectroscopy.1 Trichodiene (1) has been shown to be the biogenetic precursor of the trichothecane family of sesquiterpenoids as characterized by the cytotoxic fungal metabolite (-)-trichodermin (2).2,3 The structure and absolute stereochemistry of (-)-trichodermin (2) were determined by X-ray diffraction and, therefore, the structure and absolute stereochemistry of trichodiene (1) are now firmly established.4 We wish to report a total synthesis of (±)-trichodiene (1) via previously reported lactone 3.5,6 相似文献
3.
Recently some furanonaphthoquinones were isolated from Tabebuia species2,3,4. The structures la, lb2, and li4 were assigned to three of these compounds (those of la and lb being later confirmed by synthesis3,5,6). However, for the three other isolated compounds the spectroscopic data did not permit a decision to be made between the 2,3,4 - - - 4 isomeric pairs of structure lc and Id, le and lf 3, and lg and lh 4. Compounds la, lb, and le (or If), were tested in the KB cell culture assay and shown to be more active cytotoxic agents than lapachol2,3, the probable biogenetic precursor of all of them. 相似文献
4.
We recently reported a facile synthesis for bicyclo-[n.2.0]alkanediols of the general structure 1. 1 The recent demonstration2 that cis-bicyclo[3.2.0]heptane-1,7-diol(3) can be converted to the novel, highly-strained trans-bicyclo[4.1.0]heptane system increases the interest in this class of compounds. Comparison of our diols with materials used by Paukstelis and Kao in the rearrangement studies2 and further work in our laboratory has shown that the diols reported in our initial communication are trans-diols and should be assigned structures 4 and 5. 相似文献
5.
Tsutomu Tsuchiya Yoshiaki Takahashi Makoto Endo Sumio Umezawa Hamao Umezawa 《Journal of carbohydrate chemistry》2013,32(4):587-611
2′,3′-Dideoxy-2′-fluorokanamycin A (23) was prepared by condensation of 6-azido-4-0-benzoyl-2,3,6-trideoxy-2-fluoro-α-D-ribo-hexopyranosyl bromide (13) and a protected disaccharide (19). Methyl 4,6-0-benzylidene-3-deoxy-β-D-arabino-hexopyranoside (5) prepared from methyl 4,6-0-benzylidene-3-chloro-3-deoxy-β-D-allo-hexopyranoside (1) by oxidation with pyridinium chlorochromate followed by reduction with Na2 S2O4 was fluorinated with the DAST reagent to give methyl 4,6-O-benzylidene-2,3-dideoxy-2-fluoro-β-D-ribo-hexopyranoside (7). Successive treatment of 7 with NBS, NaN3 and SOBr2 gave 13. The structure of the final product (23) was determined by the 1H and 19F and shift-correlated 2D NMR spectra. 相似文献
6.
Abstract The well-known tricyclic sesquiterpenoid (?)-sativene, isolated in 1965 from Helminthosporium sativum and shown to possess structure and absolute configuration as indicated by structure 1 3, has been implicated3,4 as an intermediate in the biogenesis of the fungal toxin (?)-helminthosporal (2)5. Two total syntheses of the racemic modification of sativene have been reported6,7. A closely related sesquiterpenoid, (+)-cyclosativene, was isolated from Abies magnifica A. Murr. and was shown to possess structure 3 8,9. The absolute configuration of this material, although not established unambiguously, has been proposed10 as indicated by formula 3. The total synthesis of cyclosativene has not as yet been achieved directly, although it has been obtained indirectly via acid-promoted rearrangement of sativene8,9,11,12. We report herein a total synthesis of (+)-sativene (4) and (+)-cyclosativene (3) via a stereoselective route which unambiguously establishes the absolute configuration of both natural products. 相似文献
7.
Abstract The reaction of N-phenyliminoketenylidenetriphenylphosphorane [a] (1), with 2-benzylidene-1, 3-indandione (2), 1,2-diphenyl-3,4-pyrazolidenedione (3)and/or 5-benzylidene barbituric acid (4) has been investigated. When ylide 1 was allowed to react with compounds 2, 3 or 4 in THF at ambient temp. the corresponding new pyrano-phosphoranylidenes 5, 6 or 7 were obtained. The elemental microanalyses, IR, 1H NMR, 31P NMR and MS data agree with the structure of the cyclic iminophosphoranes by [4+2]-cycloaddition and exclude 4-membered ring structure by [2+2]-cycloaddition. When the Wittig reaction was carried on the pyrano-phosphoranes 5, 6 or 7 using p-nitrobenzaldehyde, the exocyclic olefins together with triphenylphosphine oxide were isolated. 相似文献
8.
As a part of our studies in the conversion of triterpenoids into steroids we have reported1 that the Jones oxidation of some triterpenoid hemiacetals (1) gives acyloxy acids (2) instead of the desired 1,5-diketones (3). We now report2 the shortest route yet for the reconstruction of a triterpenoid ring A ketone (4) into a steroidal enone (7) involving as key steps the exhaustive Baeyer-Villiger oxidation3 of triterpenoid ketones (4) into δ-lactones (5) and mild chromium(VI) oxidation of cyclic hemiacetals (1) into diketones (3). 相似文献
9.
Several years ago a number of antihypertensive N-alkyl-N′-cyano-N″-pyridylguanidines was prepared by addition of cyanamide to N-alkyl-N′-pyridylcarbodiimides which were obtained from the respective thioureas and phosgene or triphenylphosphine/carbon tetrachloride1. Recently we have described some attractive synthetic methods for N-alkyl-N′-4-pyridylthioureas2, based on 4-pyridyldithiocarbamic acid (1) (Scheme 1). We now report on the synthesis of N-alkyl-N′-cyano-N″-4-pyridylguanidines (4) from (1) by two different routes which ultimately may pass through a common intermediate (3) (Scheme 1). 相似文献
10.
In 1972 we proposed1 structure 3 for flavipucine, an antibiotic from an Aspergillus flavipes strain. Later we reported2 a novel reaction of 6-methyl-4-hydroxy-2-pyridone with α keto aldehydes which provided 1a from isobutylglyoxal and it was stated that we believed 1a would serve as a key intermediate in the total synthesis of flavipucine 3. 相似文献
11.
Ernst Peter Müller Paul Peringer Roland Aeschimann Thomas Maetzke Walter Petter 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4)
Abstract Reaction of the 2-azidoalcohol 1 with 2-phenyl1-1,3,2-dioxaphospholane leads to a 4:1 mixture of the pentacoordinate phosphorane 3 and the diazadiphosphetidine 4. In solution, these compounds are in equilibrium, presumably involving the not detectable iminophosphorane 2. A single X-ray analysis carried out on 3 proves the structure of this type of compound which has been postulated earlier as intermediate in the synthesis of aziridines from azidoalcohols1,2 相似文献
12.
Trichodiene (1), a sesquiterpene hydrocarbon, was isolated and characterized by Nozoe and Machida in 1970.1 Trichodiene (1) has been shown to be the biogenetic precursor of the trichothecane family of sesquiterpenoids characterized by the cytotoxic fungal metabolite (–)-trichodermin (2).2,3 We recently reported a total synthesis of (±)-trichodiene (1) via lactone 3.4 Now, we wish to report another stereoselective total synthesis of (±)-trichodiene (1) via lactone 3 which is highly regioselective. 相似文献
13.
For many years the synthesis of diterpene acids has attracted the attention of organic chemists. Kröniger and Wheeler1 reported that the condensation of the dimethylate 1a with methyl malonate gave the cis compound 2a which on heating with palladised charcoal was converted into the trans isomer 3a. Compound 3a is a promising intermediate in the synthesis of derivatives of both abietic and podocarpic acids, while 2a could be a starting material for the synthesis of cis fused diterpene acids. However, the route to 2a and 3a was inefficient; 1a was only available as the minor component of a mixture with its epimer 1b; and the yield for the stage 2a + 3a was poor. 相似文献
14.
α-Bromoacetals (1) are valuable precursors in synthesis of α,β-unsaturated carbonyl compounds (2), 1-alkoxybutadienes2 (3), ketene acetals3 (4), 2-methoxyallyl bromides4 (5) and other compounds. Because of our interest in the chemistry5,6 of 3 and 4 we attempted to improve known procedures for the preparation of 1 with the aim to get a short and efficient synthesis of these compounds. 相似文献
15.
Abstract Glycosylation of methyl 3-O-(2-acetamido-3, 6-di-O-benzyl-2-deoxy-β-D-glucopyranosyl)-2,4,6-tri-O-benzyl-β-D-galactopyranoside (2) with 2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl bromide (1), catalyzed by mercuric cyanide, afforded a trisaccharide derivative, which was not separated, but directly O-deacetylated to give methyl 3-O-(2-acetamido-3,6-di-O-benzyl-2-deoxy-4-O-β-D-galactopyranosyl-β-D-giucopyranosyl)-2,4,6-tri-O-benzyl-β-D-galactopyranoside (8). Hydrogenolysls of the benzyl groups of 8 then furnished the title trisaccharide (9). A similar pflyccsylation of methyl 3-O-(2-acetamido-3-O-acetyl-2-deoxy-β-D-glucopyranosyl)-2,4,6-tri-O-benzyl- β-D-galactopyranoside (obtained by acetylation of 4, followed by hydrolysis of the benzylidene acetal group) with bromide 1 gave a tribenzyl trisaccharide, which, on catalytic hydrogenolysls, furnished the isomeric trisaccharide (12). Methylation of 4 and 2 with methyl iodide-silver oxide in 1:1 dichloro-methane-N, N-dimethylformamide gave the 3-O- and 4-O-monomethyl ethers (13) and (15), respectively. Hydrogenolysis of the benzyl groups of 13 and 15 then provided the title monomethylated disaechartdes (15) and (16), respectively. The structures of trisacchacides 9 and 12, and disaccharides 14 and 16 were all established by 13C MMR spectroscopy. 相似文献
16.
In 1977 Tamaki1 et al have isolated and synthesized2 (Z)-7-nonadecen-ll-one (la) and (Z)-7-eicosen-l1-one (1b) which are active components of the female sex pheromones of the peach fruit moth Carposina niponensis Walsingham, a major economic pest of apple, peach and other fruits of Japan. We report in this communication a practical, convenient and stereospecific route to 1a and 1b. 相似文献
17.
George P. Rizzi 《合成通讯》2013,43(14):1173-1179
A wide variety of 2′-hydroxypolymethoxyacetophenones and propiophenones, e.g. 1a and 1b are used in the synthesis of flavone and ehromone natural products.1 Repeated attempts to prepare 1a and 1b by reacting 1,2,3,5-tetramethoxybenzene 2 with acetyl or propionyl chlorides and AlCl3 in ether2 gave products which were difficult to purify.3 We traced the problem to ring-ethoxy contaminants which were isolated and tentatively identified as 3a and 3b. 相似文献
18.
The usefulness of diimidazoles2 such as N, N′-carbonyldi-imidazole (1), and N, N′-thionyldiimidazole (2) in organic synthesis has been accumulated recently. In connection with the continuing our studies on the reaction using 1 or 2 3 (carbonyl, thionyl, and imidazole transfer reactions), our particular interest was focused on the synthesis of N-(chlorosulfinyl)-imidazole (3) in which one imidazole group in 2 was replaced by the other leaving group (Cl). Also, 3 was interesting for preparative purposes as a chlorine atom could be introduced via the addition reaction of 3 to carbonyl compounds as known in the reaction of 1 or 2 with ketones. 相似文献
19.
A useful synthesis of 3-hydroxy-4-chromanone (6) is not currently available. Lead tetraacetate oxidation of 4-chromanone (4) yields the C(3) acetoxy derivative but this compound could not be deacetylated to 6.1 Recently Donnelly and Maloney reported2 that the Algar-Flynn-Oyamada reaction (H2O2/CH3OH/NaOH), which is commonly used for the conversion of o-hydroxychalcones (1) into 3-hydroxyflavanone (2) and 3-hydroxyflavones (3), does not yield 6 when applied to o-hydroxya-crylophenone 1 (R = H). The authors found that under less basic conditions using K2CO3 some 6 is formed but the major product is catechol. These observations clearly indicate the necessity of developing a method for making 6. The present note describes a staightforward way of preparing 3-hydroxy-4-chromanone (6) in good yield. 相似文献
20.
Lydia Lamande Aurelio Munoz Danielle Boyer Bernard Garrigues Robert Wolf 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-3):85-88
Abstract The crystal structure of the triethylammonium salts of hydroxyphosphoranes 1a and 2 was resolved by X Ray diffraction. The first one has a TBP geometry slightly deformed with the phosphorus atom at the center, and the second one is a polycylic dimer containing two TBP which present the same deformations. In both cases, the P-O? bond lengths are short and dioxaphospholane rings planar. These two particular properties can be related to the strong Bronsted acidity of compounds 1a and 2. Effectively, the pKa of hydroxyphosphoranes 1a, 1b and 2, determined by potentiometrical titration in DMF or DMSO solutions are characteristic of strong acids. 相似文献