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1.
The α-anions of 2-substituted 1,3-dioxolan-4-ones derived from chiral mandelic and lactic acid (, ; ; , ) were alkylated with high stereoselectivity. The products formed were hydrolysed to α-hydroxy acids with 65–85% e.e. ((S)(+)-,,, (R)(–)-). 相似文献
2.
Yasuo Sakai Shingo Toyotani Yoshito Tobe Yoshinobu Odaira 《Tetrahedron letters》1979,20(40):3855-3856
Oxidative decarboxylation of [n.2.2]propellane carboxylic acids (-) with lead tetraacetate gave the bicyclic acetates (, ) having a bridgehead double bond and/or the tricyclic acetates (, ) in good yields. Vapor phase thermolysis of or afforded the bridgehead olefin or quantatively. 相似文献
3.
N,N-Dimethylformamide () and N,N-dimethylpivalamide () react with carbonyl chloride isocyanate () in the presence of antimony pentachloride to afford the amino substituted 1-oxa-3-azabutatrienium hexachloroantimonates ,. An X-ray diffraction analysis of confirms the proposed structure. The heterocumulenes , react with aldehydes, ketones and tertiary carboxamides to give the amino substituted 2-azaallenium salts - in high yields. 相似文献
4.
6, 7-Dimethoxy-2-l,3-benzothiazine derivatives (, ) react with substituted acetyl chlorides to give angularly condensed β -lactams (-, , ). The compound was epimerised to the derivative . From the interaction of 2-phenyl-6,7-dimethoxy-4-1,3-benzothiazine () and α -chloro-phenylacetyl chloride two stereoisomeric β -lactam derivatives (, ) were isolated, whereas in the other cases studied the reactions leading to β -lactams proved to be stereospecific. Analogous reactions of -methyl-6,7-dimethoxy-2-l,3-benzothiazine () furnished the enamides ,, . Structures of the new compounds and configurations of the diastereomers were elucidated by IR and NMR spectroscopy. 相似文献
5.
Roshantha A.S. Chandraratna Robert R. Birge William H. Okamura 《Tetrahedron letters》1984,25(10):1007-1010
The electronic absorption spectra of the four new 12---locked retinals (1a–1d) bearing 7-, 11- double bond geometries are described and compared with those of analogous 7-, 11--geometries (1e–1h) and parent retinals (2a-h). 相似文献
6.
《Tetrahedron》1986,42(13):3623-3629
The synthesis of ()-13-fluorohexadec-13-en-11-ynyl acetate , a fluorinated analog of the sex pheromone of the processionary moth Thaumetopoea pityocampa is described. The synthetic scheme involves epoxidation of the double bond, regioselective opening of the oxirane ring with Olah's reagent, tosylation of the resulting fluorohydrin and dehydrotosylation. Structural features of the intermediate diastereomeric fluorohydrins and and tosylates and are also discussed on the basis of their 1H and 19F NMR spectra. 相似文献
7.
Martine Bonin José R Romero David S Grierson Henri-Philippe Husson 《Tetrahedron letters》1982,23(33):3369-3372
The cis 2,6-dialkylpiperidine alkaloid (±) dihydro-pinidine and the trans alkaloid (±) solenopsin A were synthesized from a common α-aminonitrile synthon . The key step in this synthesis was the stereoselective reductive decyanation of the 1-benzyl-2cyano-2′, 6-dialkylpiperidines and . 相似文献
8.
For 12-- locked retinal analogues, thermal equilibria are established between 11-, 13--1c and 13--2c and between 9-, 11-, 13--1d and 9-, 13--2d; a photoisomerization occurs to transform 2c to --2a and 2d to 9--2b 相似文献
9.
《Tetrahedron: Asymmetry》2000,11(5):1109-1122
A mixture of cis- and trans-2-(6-m-methoxyphenyl-3-oxohexyl)-2,4-dimethylcyclopenta-1,3-dione (±)-10 was synthesized and incubated with Schizosaccharomyces pombe (NRRL Y-164) to give (+)-11, (+)-12, (−)-13, and (−)-14 in 19, 13, 22, and 16% yields, respectively. Chromic acid oxidation of these microbiologically reduced products gave (−)-10a, (+)-10b, (+)-10a, and (−)-10b, respectively. 相似文献
10.
Methyl 5(S), 6(S)-oxido-11-oxo-7-cis-9-trans-undecadienoate was prepared and used for the synthesis of the novel 7-cis-LTD4 () as well as, after isomerization to the all-trans dienal ester , for that of the natural leukotrienes. 相似文献
11.
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
12.
Alkylation of the distal double bond of pseudoionone has been carried out with isoprene epoxide (ZnCl2 /MeNO2 ) leading directly to α-, α- and γ hydroxyprenylionones. The α- and γ-isomers have been converted in few steps into the C50 carotenoids decaprenoxanthin and C.p. 450 respectively. 相似文献
13.
Photolysis of the N-[ω-(cycloalken-1-yl)alkyl]phthalimides 6b- in each case gave a pair of stereoisomers of spiro-nitrogen multicyclic systems (9b-) in moderate yields, whose stereochemistry was determined by means of chemical and spectroscopic analyses. Similarly, in N-[ω-(inden-3-yl)alkyl]-phthalimides (8), spiro-nitrogen macrocycles up to 13-membered 13a- were obtained in good yields 相似文献
14.
In the presence of 1-methylimidazole, 2--acyl guanine (as in ), thymine (as in ) and uracil (as in ) residues react readily with the phosphorylating agent derived from 2-chlorophenyl phosphorodichloridate () and 1-hydroxybenzotriazole. 相似文献
15.
16.
The rate of the thermal rearrangement of (S) 2 chloromethyl-1-ethylpyrrolidine [(S)-1a] to (R)-3-chloro-1-ethylpiperidine [(R) 2a] has been examined at three temperatures in benzene by PMR and polarimetry. The rearrangement was shown to be completely stereospecific and to obey a simple first order rate law. The calculated Ea ΔH3 and ΔS3 were 22 ± 2 (25°), 21 ± 2.5 (25°) and - 10 ± 2 e.u. (0°K) respectively. The effect of solvents having differing dielectric constants was also studied. A transition state 9'a and an ion pair intermediate 3a are suggested for the rearrangement. The stereochemical course of the reactions of (S)-1a, (R)-2a and (S)-2a with hydroxide and methoxide ions have been shown to be 100% stereospecific with an uncertainty of about 1%. The absolute configurations of all optically active reactants and products [(S)- and (R)-4a, (S)-4b (R)- and (S)-5a, (R)-5b, (S,S')-6a, (S,R')-7a and (R,R')-8a] were established by chemical correlations with known compounds or by ORD and chemical inference. The ring opening of both the primary and secondary aziridinium ion positions of 1-azonia-1-ethylbicyclo [3.1.0]hexane [(S)-3a] by nucleophiles proceeds entirely by SN2 processes. The conversion of (R)-1-ethyl-3-hydroxypiperidine [(R)-5a] to (S)-2a. HCl with thionyl chloride in chloroform proceeds by inversion with 4.8% racemization, whereas the thermal rearrangement of (S)-1a to (R)-2a occurs with complete retention of absolute configuration. 相似文献
17.
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
18.
A short route to the 2-azabicyclo[3.3.1]nonan-7-one system is described. Condensation of 4-piperidones with diethyl 2-oxopropylphosphonate, followed by catalytic hydrogenation furnished the corresponding piperidylpropanones which were cyclized with mercuric acetate in acetic acid to the target target bicyclic ketones . The Fischer indole synthesis from afforded regioselectively the indole [3,2-f]morphan , a new heteromorphan type. 相似文献
19.
H. Rönsch 《Tetrahedron》1981,37(2):371-375
The trans lactole alpinigenine (1a) isolated from Papaver bracteatum Lindl. was shown to form the oxime 2a which in turn was transformed to the nitrile 3a by dehydration, the methiodide 4a, and — by treatment with alkali under mild conditions — to the benzylidene phthalimidine derivative 5a, whose structure was elucidated by spectral analysis as well as oxidative fragmentation into 6 and 7.The unique reaction leading to 5a apparently is bound with certain structural prerequisites inherent to 3a, including stereochemistry. When cis-alpinigenine (1b) was subjected to the same sequence, little of 5a accordingly could be obtained, and even none of any phthalimidine was formed from the non-acetoxylated nitrile 11. 相似文献
20.
Isao Kawada Mitsuko Nakano-Onoda Motohiko Ishii Masanobu Saeki Mitsuoki Nakahira 《Journal of solid state chemistry》1975,15(3):246-252
Crystal structures of the ordered phases of V3S4 and V5S8 were refined with single crystal data. Both are monoclinic. Chemical compositions, space groups and lattice constants are as follows: VS1.47, (No. 12), a = 5.831(1), b = 3.267(1), c = 11.317(2)Å, β = 91.78(1)° and VS1.64, (No. 12), a = 11.396(11), b = 6.645(7), c = 11.293(4), Å, β = 91.45(6)°. In both structures, short metal-metal bonds were found between the layers as well as within them. In comparison with the structure of Fe7S8, the stability of NiAs-type structure was discussed based on the detailed metal-sulfur distances. 相似文献