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1.
Jack E. Baldwin Robert M. Adlington Bernard J. Rawlings Richard H. Jones 《Tetrahedron letters》1985,26(4):485-488
Practical procedures for the resolution of racemic modification of (1, 2)-and (1, 2)-1-amino-2-ethylcyclopropane-1-carboxylic acid ,,(1, 2)- and (1, 2)-1-amino-2-methylcyclopropane-1-carboxylic acid ,, and (1, 2)- and (1, 2)-1-amino-2-methylcyclopropane-1-carboxylic acid , are described; the structures as ,, and were confirmed by X-ray-crystallographic methods. 相似文献
2.
The synthesis of the 2,4,6-cycloheptatrienyl ketones – by two alternative routes is reported: Route 1): The adducts from the phenyl(trimethylsiloxy)-acetonitriles , known as “umpolung” reagents, and tropylium tetrafluoroborate are cleaved by triethylammonium fluoride to form the aromatic cycloheptatrienyl ketones –. Route 2): the phenyl, methyl, and cyclopropyl ketone (, , ) are prepared by treatment of the acid chloride with the corresponding organomanganese iodides RMnI (, , ). The Fe-catalyzed coupling reaction of the acid chloride with a Grignard reagent was also used for the preparation of ketone . 相似文献
3.
The addition of phenylhydrazine to phenylazo-alkenes yields α-(1-phenylhydrazino)-phenylhydrazones . The reaction of phenylhydrazine with α-halogenated carbonyl compounds affords either or the isomeric α-(2-phenylhydrazino)-phenylhydrazones . Structures and (>N-NH2 and-NH-NH- groups, respectively) can be differentiated by 1H NMR in DMSO-D6 solution. Possible pathways of the reactions leading to either or are discussed. Compounds are found to be precursors of phenylosazones . 相似文献
4.
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
5.
The - and -2-amino-4-cyclohexene-1-carboxylic acids and react with imidates to give the condensed-skeleton, bicyclic - and -pyrimidin-4-ones and . The amino acids and were reduced to the -and -1, 3-aminoalcohoIs and , which were cyclized by means of imidates to the bicyclic tetrahydro-4-3,1-benzoxazines and , or were converted, the corresponding carbamates and into the tetrahydro-4-3,1-benzoxazin-2(1)-ones and . The 2-thioxo analogues and were prepared by cyclization of the dithiocarbamates obtained from the aminoalcohols and by treatment with carbon disulphide. The -aminoalcohol and its saturated analogue reacted with -chlorobenzaldehyde to furnish the hexahydro and octahydro-4-3,1-benzoxazine , respectively. 1H and 13C NMR studies showed that, similarly to the earlier-investigated analogues containing oxygen or unsubstituted nitrogen at position 1, the synthesized isomrs , , and occurred as the preferred conformer in the heterocyclic twist inverse form of -inside type ( C6-N bond) (B). In the isomers containing a saturated C-2 atom ( and ), H-2 and H-6 are in relative positions. 相似文献
6.
Reduction of the indole-1-carboxaldehydes (-) with borane /THF gives the 1-methylindoles () in 42-91-% yields together with the di(indolylmethyl)ethers (), the indolyl-methyl indolines (), the unsymmetric ether() and the indolenine () as the minor products, except . This appears to be the first report on the formation of symmetric ethers in the borane/THF reduction of an oxygen function. The formation of and from and implies that electrophilic substitution takes place primarily at position 3 of 3-substituted indoles, did not form the corresponding probably because of steric hindrance. These results are discussed in relation to the mechanisms of borane/THF reduction, origin of the different products and electrophilic substitution in 3-substituted indoles. 相似文献
7.
The geometries and the 1H chemical shifts of dihydropyrene and its benzannelated derivatives – have been studied by means of semiempirical quantum chemical procedures. The calculated bond lengths of and proton shifts of – are in good accord with the corresponding experimental values. We show that monobenzannelation in – causes considerable bond length alternation in the [14] perimeter and hence reduced diatropocity. The same is true for the phenanth-fused dibenzannelated compounds and . On the other hand we report evidence that anth-fused dibenzannelated dihydropyrenes , , and should be characterized by symmetric geometrical structures without significant bond length alternation thus leading to enhanced diatropicity. 相似文献
8.
Z-1-Methoxybutenyne was used for the synthesis of Z,E-1-methoxybutadiene derivatives –. Hetero-Diels-Alder reactions with diethyl mesoxalate led to the C-4 branched pseudoglycals –, and to the glycal , respectively. The bicyclic lactone was obtained by dealkoxycarbonylation of . 相似文献
9.
《Tetrahedron》1986,42(21):5985-5990
The title compounds, and ', are readily available in four steps from 2-benzyloxymethyl-2-propen-1-ol, the key step being Sharpless asymmetric epoxidation to give the chiral epoxides or '. The total chemical yield of or ' is 50%, the final products being obtained essentially optically pure. By suitable protecting group manipulation, both title enantiomers can be produced from either of the antipodal epoxides or '. 相似文献
10.
Ratna Dasgupta Pranab R. Kanjilal Swapan K. Patra Manish Sarkar Usha Ranjan Ghatak 《Tetrahedron》1985,41(23):5619-5625
The efficacy of a new acid-catalyzed intramolecular C-alkylation has been demonstrated by the synthesis of 1-methyl-4--methoxyphenylbicyclo [2.2.2] octan-2-one () and 4--methoxyphenylbicyclo [2.2.2] octan-2-one () from easily accessible starting materials. The carbinol , derived from , undergoes facile rearrangement leading to 1--methoxyphenyl-4-methyl bicyclo [3.2.1] oct-3-ene (), which has been transformed to -1--methoxyphenyl-4-methylbicyclo [3.2.1] octan-3-one (). 相似文献
11.
(1,l-Dihydroperfluoroalkyl)phenyl- and --fluorophenyliodonium triflates and were synthesized by the reaction of l-bis(trifluoroacetoxy)iodo-1,l-dihydroperfluoroalkanes with triflic acid and benzene or fluorobenzene in 1,1,2-trichlorotrifluoroethane. The use of fluorosulfonic acid and sulfuric acid instead of triflic acid afforded (1,l-dihydroperfluoroalkyl) phenyliodonium fluorosulfonate and sulfate , respectively. Similarly, (1,1,ω-trihydroperfluoroalkyl)phenyliodonium triflate and 1,1,5,5-tetrahydroperfluoropentane-l,5-bisphenyliodonium triflate were synthesized. 相似文献
12.
《Tetrahedron letters》1987,28(16):1821-1824
Acid-catalysed hydrolysis of 2,2-dimethoxy-3,4-dihydropyrans () yields mixtures of δ-keto esters () and 3,4-dihydro-α-pyrones (). The amount of increases with increasing alkyl substitution in the 3-, 5- and 6-position of and when the hydrolysis is carried out in a two-phases system of water/dichloromethane. It is shown that is formed directly from whereas is formed directly from and by methanolysis of . The mechanistic and synthetic aspects of these hydrolysis reactions are discussed. 相似文献
13.
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
14.
The readily-obtained carbohydrate α-enones , and are converted into the four diastereomeric 2,4-di-C-methyl glycopyranosides ,,, which are chiral synthons for the four multistriatins -. 相似文献
15.
Three different types of butanolide complexes with EtnAlCl3?n in the molar ratios and have been investigated by IR with 1M NMR spectroscopy. The butanolides form and complexes with ethylaluminium halides, but with triethylaluminium only complexes are formed. The complexes are intermediates in the cleavage of butanolides. 相似文献
16.
The synthesis of 3-acetylcyclohexanones , , has been realized by conjugate addition of lithiated cyanohydrin ether to 2-cyclohexenones , , in THF-HMPA, even if 3-substituted. 3-benzoylcyclohexanones , , are obtained from and , , in THF with excellent yields. 相似文献
17.
Several π-excessive heteropolyaromatic compounds, which contain furan and thiophen ring and are possible antifungal agents, have been synthesized in good yields according to two general methods. The first method has been used to prepare compounds possessing thiophens linked by their 2- and 5-positions, such as the ter-aryls , and . Two precursors of these compounds have been obtained either by the Glaser reaction, or using a novel Pd-mediated reaction. The second method,which consists of the Ni-or Pd-catalyzed heteroarylation of heteroarene halides via cross-coupling with heteroaryl Grignard reagents or zinc halides,has been used to prepare the bi-aryls , which contain two heteroaromatic units, and the ter-aryl . Compound has been also prepared starting from 2-(2-thienyl) furan () by selective lithiation, followed by bromination.The 13C NMR signals of and have been assigned on the basis of the literature data and by relaxation measurements. Relaxation data have been also used to obtain qualitative informations on the conformational equilibria of the bi-aryls , and the ter-aryls . 相似文献
18.
Paul von Ragué Schleyer Peter Grubmüller Wilhelm F. Maier Otto Vostrowsky Lars Skattebøl Kjetil H. Holm 《Tetrahedron letters》1980,21(10):921-924
Tricyclo(4.2.2.o1,5)decane () in the presence of AlBr3 rearranges partly “forwards” to adamantane () and partly “backwards” to tetrahydrodicyclopentadiene (, largely the oxo isomer). Intermediate , characterizing the →exo-→→→ forward pathway, is found only in small amounts. The detection of a new intermediate, , also shows that a second major rearrangement route from to is being utilized (see dashed lines in Figure 1). 相似文献
19.
Alcohols and , prepared from , underwent completely stereospecific etherification to give 1-oxacephams and , which were converted into the 1-oxacephem nucleus via and . Functionalization at C-3′ in and was unsuccessful. 相似文献
20.
Isomerization of -bicyclo[10.8.0]eicos-1(12)-ene () and -bicyclo[10.10.0]docos-1(12)-ene () to [10.8]- and [10.10]betweenanene ( and ) has been effected by sulfuric acid. In both cases, the betweenanene isomers were found to predominate at equilibrium (70/30 / and 95/5> /). 相似文献