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1.
The cycloaddition of α,β-epoxyaldehydes or ketones () with the ketene acetal MeHC=C(OMe)2 () gives epoxyoxetanes () in high yields. Without isolation they can be transformed into 4-hydroxy-5-(1-hydroxyalkyl)-γ-butyrolactones () via the epoxy esters and trihydroxy esters (). The lactones appear to be valuable precursors for the synthesis of 5-(1-hydroxyalkyl)-3-methyl-2-5H-furanones () and 3-methyl-5-ylidene-2-5H-furanones () 相似文献
2.
Two new tetrahydropyrans have been isolated from the sponge Haliclona sp. From chemical and spectroscopic evidence they are shown to be (1′, 2, 2″, 5, 6)-2-(1′-bromethyl)-2,5-dimethyl-6-(penta-2″,4″-dienyl)-tetrahydropyran and (1′, 2, 5, 6)-2-(1′-bromoethyl)-2,5-dimethyl-6-(pent-4″-enyl)-tetrahydropyran. 相似文献
3.
Titanium(IV) chloride-mediated reaction of 4,5-dihydro-2-(trimethylsiloxy)-3-(trimethylsilyl)furan (1a) with acetaldehyde gave (3S*, 1′R*)-4,5-dihydro-3-(1′hydroxyethyl)-3-(trimethylsilyl)-2(3)furanone (2a), which afforded selectively either (Z)- or (E)-α-ethylidene-γ-butyrolactone (3a) under proper conditions. Facile isomerization of 2a into (3S*, 1′R*)-4,5-dihydro-3-&{1′-(trimethylsiloxy)ethyl}-2(3)furanone (4) suggests an intriguing stereochemical outcome from 2a to (E)-3a via an enolate of 4. 相似文献
4.
A synthesis of (2S,3S,7S)-3,7-dimethylpentadecan-2-yl acetate () and propionate () is described. (2S)-2-Methyldecan-1-yl lithium () was reacted with (3S,4S)-3,4-dimethyl-γ-butyrolactone () to yield the ketoalcohol which upon Huang-Minlon reduction furnished (2S,3S,7S)-3,7-dimethylpentadecan-2-ol (). Acylations gave the esters and . The (2S)-2-methyldecan-1-yl lithium was obtained via asymmetric synthesis. The chiral lactone was obtained from (2S,3S)-trans-2,3-epoxybutane and dimethyl malonate. 相似文献
5.
Asymmetric cyclizations of methyl (E)-3-oxo-9-phenoxy-7-nonenoate () or methyl (E)-3-oxo-9-(methoxycarbonyl)oxy-7-nonenoate () without added base were carried out in the presence of a catalytic amount of palladium(II) acetate and chiral diphosphine as ligands. Allylic carbonate reacted by use of Pd(OAC)2-(S)-(R)-BPPFA at room temperature to give (R)-3-vinylcyclohexanone (), after decarboxylation, in up to 48% e. e. 相似文献
6.
Masamichi Maruta Satoshi Kubota Narihiko Yoshimura Tomoya Kitazume Nobuo Ishikawa 《Journal of fluorine chemistry》1980,16(1):75-88
4-Fluoro-2-(-ethyl)-3-(-methyl)-1, 5-benzoxazepine was prepared by reaction of -2-methyl-2-pentene with 2-aminophenol in the presence of triethylamine in diethyl ether. The reaction of -2,4-dimethyl-3-heptene with 2-aminophenol in dimethylformamide gave 7-(-1-methylethyl)-8- (-ethyl)-9,14-benzoxazepino[4,3-b]1,6-benzoxazepine. Several ortho-bifunctional benzenes reacted similarly with -2-methyl-2-pentene and -2,4-dimethyl-3-heptene to give the corresponding seven-membered benzoheterocycles. 相似文献
7.
E.G. Frandsen 《Tetrahedron》1977,33(8):869-873
The reaction of 4- and 5-aryl-3-methylthio-1,2-dithiolylium iodides with 4-hydroxy-6-methyl-2-pyran-2-one and 4-hydroxycoumarin has been studied. 4-Substituted salts yielded 3-aryl-7-methyl-2-thioxo-2,5-pyrano [3,2-c]pyran-5-ones and 3-aryl-2-thioxo-2H,5H-pyrano[3,2-c]benzo[e]pyran-5-ones, respectively, whereas 5-substituted salts gave rise to 3-(5′-aryl-1′,2′-dithiol-3′-ylidene)-6-methyl-2-pyran-2,4-diones and 3-(5′-aryl-1′,2′-dithiol-3′-ylidene)-2-benzo [b]-pyran-2,4-diones. 相似文献
8.
Wolfgang Oppolzer Mark Kurth Daniel Reichlin Frank Moffatt 《Tetrahedron letters》1981,22(27):2545-2548
The chiral induction in the Diels-Alder addition → , assessed reliably by 19F-NMR-spectroscopy of the endo-esters , varied between 47 - 93% in favor of the 2-(R)-adducts depending on the auxiliary chiral group and the Lewis-acid catalyst. 相似文献
9.
《Tetrahedron》1987,43(13):3021-3030
A new synthesis of 9,10-dimethoxy-1,3,4,6,7,11b-hexahydro-2H-benzo aquinolizin-2-one ( and its 3-ethyl derivative via the corresponding 2-(3,4-dimethoxyphenyl)-4-piperidone ethylene acetals is reported. Alkylation of 2-arylpipendires with 2-bromoethanol followed by oxidation of the resulting amino alcohols with oxalyl chloride and dimethyl sulfoxide afforded the aldehydes , which were cyclized with hydrochloric acid to give 7-hydroxybenzo[α]quinolizidines . The reduction of with trinethylsilane and subsequent acid hydrolysis led to benzo aquinolizidin-2-ones . 相似文献
10.
In an attempt to prepare short-bridged hydroxymetacyclophanes , the spirocyclohexadienones were pyrolyzed by flash vacuum thermolysis (FVT). Instead of , variable amounts of 4-(5-hexenyl)phenol (), β-hydroxybenzocycloalkenes () and 4-(trans-1-alkenyl) phenols () were obtained. The formation of these products is explained by invoking cleavage of a spiro bond in under formation of the intermediate diradical which, depending on the length of the aliphatic chain and on the temperature, has several pathways open for isomerization to spin-paired products. 相似文献
11.
2-Hydroxybenzoic acid heated with 2,4 - bis(4 - methoxyphenyl) - 1,3,2,4 - dithiadiphosphetane - 2,4 -disulfide, 1, gave 2 - (p - methoxyphenyl) - 4 - 1,3,2 - benzoxathiaphosphorin - 4 - one 2 - sulfide, 3, and its thio-analogue, 4, while its ethyl or phenyl esters gave 4 as the sole product. 2 - Mercaptobenzoic acid and its ethyl ester when heated with 1 produced 3 - 1,2 - benzodithiole - 3 - one, 8, 3 -1,2 - benzodithiole - 3 - thione, 9, and 2- (p - methoxyphenyl) - 4 - 1,3,2 - benzodithia - phosphorin - 4 - one 2 - sulfide, 10. The reaction of 2 -aminobenzoic acid with 1 gave 1,2 - dihydro - 2 - (p - methoxyphenyl) - 4 - 3,1,2 - benzoxaphosphorin - 4 - one 2 - sulfide, 12. Reactions of 1 with methyl 2 - aminobenzoate and 2 - aminobenzamides are described. Mechanistic considerations for the formation of the heterocyclic phosphorus compounds are presented. 相似文献
12.
Thermolysis of several trans-1-isopropenyl-4-methylene-spiro[2.x]- alkanes (x = 4,5) in xylene solution at 130° causes quantitative rearrangement to 1-methylene-2-(3′-methylbut-2′-enyl)cycloalkanes ( – ). 相似文献
13.
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
14.
1-Methyl-2-(1′-cyano-1′-trimethylsilyloxy)alkyl-1H-imidazoles () were easily prepared from the corresponding stable carbonyl compounds, 1-methyl-2-acyl- 1H-imidazoles (). When the quarternary salts of were treated with various nucleophiles, reactive acyl species, which was presumed to be acylcyanide (), was generated in situ under CC bond fission to result in producing the corresponding acylated compounds (–) in good yields. 相似文献
15.
Bis(N-(1-benzoyl-2-propylidene)-2-pyridylmethylaminato)iron(III) hexafluorophosphate (Fe(bzpa)2PF6 is shown to be a spin-equilibrium compound between low- (S = ) and high- (S = ) spin states depending on temperature, and to have the unusual property that the relaxation time of the spin change is shorter than the Mössbauer lifetime (1 × 10?7s) of iron- 57 (l = ) in the solid state. 相似文献
16.
4-O-(2,6-diamino-2,3,4,6-tetradeoxy-3-C-methyl-β-L-arabino and lyxo-hexopyranosyl) and 4-O-(2-amino2,3,4,6-tetradeoxy-5-c-methyl-L-threo-hexopyranosyl-6-O-(3-amino-3-decxy-α-D-glucopyranosyl)-2-deoxystreptamine (, and ) were synthesized from a kanamycin B derivative () by regiospecific methylation and stereospecific hydrogenation followed by removal of masking groups, converting a D-sugar moiety (4-O-glycoside portion) into L-sugar. The usual conformation of and were determined as boat and skew by 250 MHz PMR spectra respectively. 相似文献
17.
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
18.
David A. Lightner Chwang Siek Pak B.Vincent Crist Stephen L. Rodgers John W. Givens 《Tetrahedron》1985,41(19):4321-4330
(lS,5S)-exo-2(R)-Methylbicyclo[3.1.0]hexan-3-one () and (lS,5S)-endo-2(S)-methylbicyclo[3.1.0]hexan-3-one (2) were synthesized and their circular dichroism (CD) spectra run. Conformational analysis based on molecular mechanics calculations and Karplus equation analyses of vicinal H¦H NMR coupling constants indicate boat-like sofa conformations for both and , with very little ring distortion from the symmetry of the parent bicyclo[3.1.0]hexan-3-one. The lone dissymmetric ψ-axial and ψ-equatorial methyl groups of and , respectively, are both octant consignate. The natural product analogs of and , (?)-3-isothujone () and (+)-3-thujone () were prepared and examined similarly. Their α-methyl perturbers dominate the CD n-π★ Cotton effects. 相似文献
19.
Under both static and flow thermolysis conditions, several compounds with an “aspidosperma” framework rearranged to “vinca” derivatives. Thus (-)1,2-dehydroaspidospermidine () rearranged to (-) gave vincane . Compound rearranged to vincamine () and 16-epi vincamine () under either condition ; increasing the temperature resulted in formation of apovincamine () (pyrolysis) or vincamone thermolysis). 相似文献
20.
The hydroboration of cis-2-butene and cis-3-hexene with pure diisopinocampheylborane (IPC2BH) and monoisopinocampheylborane (IPCBH2), both prepared from (+)-α-pinene, were studied. In contrast to IPC2BH, which yielded R-(?)-2-butanol and R-(?)-3-hexanol in 98.4 and 94.5% optical purities, IPCBH2 yielded S-(+)-2-butanol and S-(+)-3-hexanol in 23.6 and 19.7% optical purifies respectively. PMR examination of the methanolyzed products were utilized to establish the species present in the freshly prepared and aged adduct from (+)-α-pinene and BH3 · THF. The results confirm the interpretation previously advanced for the major differences realized in asymmetric hydroboration with the fresh and aged adducts. 相似文献