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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 Sharpless asymmetric epoxidation was used for the synthesis of D--dihydrosphingosine triacetate and (2, 3, 5)-2-acetamino-5,9-dimethyl-8-decene-1,3-diol, whose 13C-NMR study coupled with biogenetic consideration enabled us to propose (2, 3, 5,13, 14)-stereochemistry for aplidiasphingosine. 相似文献
3.
Three fungal metabolites with a common structural feature as prenylated phenols were synthesized in their naturally occurring and optically active forms: ascochlorin [(2',4',1',2',6')-(-)-5-chloro-2,4-dihydroxy-6-methyl-3-[5'-(1',2',6'-trimethyl-3'-oxo-cyclohexyl)-3'-methyl-2', 4'-pentadienyl] benzaldehyde], ascofuranone [(2',6',1')-(-)-5-chloro-2, 4-dihydroxy-6-methyl-3-[7'-(3',3'-dimethyl-4'-oxo-2'-oxacyclopentyl)-3',7'-dimethyl -2', 6'-heptadienyl] benzaldehyde] and ascofuranol [(2',6',1',4')-(-)-5-chloro-2,4-dihydroxy-6-methyl-3-[7'-(3', 3'-dimethyl-4'-hydroxy-2'-oxacyclopentyl)-3', 7'-dimethyl-2',6'-hepta-dienyl]benzaldehyde ]. (+)-Ascofuranone and (+)-ascofuranol were also synthesized. By the present synthesis the absolute configuration of the natural (-)-ascofuranol was established as (1',4'). 相似文献
4.
(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
5.
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
6.
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
7.
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
8.
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
9.
Pentacoordinated aminosulphur (IV) trifluorides, R2NF3, (in this paper the lone pair in S(IV)-derivatives is always considered as a ligand) and aminosulphur(VI)-oxidetrifluorides, R2NS(O)F3, readily lose a fluoride ion to Lewis acids (AsF5, SbF5, BF3) to give sulphur-containing cationic species [R2NF2]+ and [R2NS(O)F2]+ with tetracoordinated sulphur. Tetracoordinated neutral dialkylaminosulphur(IV)-oxidefluorides, R2N(O)F, and amino-imino sulphur(IV)fluorides, R2N(=NRf)F, give three-coordinated sulphur cations [R2NO]+] or [R2NNRf]+.The three-coordinated sulphur(VI)cation [R2NS(O)NR]+ has also been formed. 相似文献
10.
Kenji Mori Hiroko Nomi Tatsuji Chuman Masahiro Kohno Kunio Kato Masao Noguchi 《Tetrahedron letters》1981,22(12):1127-1130
The absolute configuration at C-6 and C-7 of serricornin was established as (6, 7) by synthesizing its (6, 7- and (6, 7- isomers. 相似文献
11.
(3,6)-(?)-3-Hydroxy-1,7-dioxaspiro[5.5]undecane 3a and its antipode were synthesized from ()-malic acid. 相似文献
12.
An efficient, highly stereoselective synthesis of (1,3)--chrysanthemic acid 6 is described. The crucial step of this synthesis was the microbiological reduction of dione 1 into ()-ketol 2. 相似文献
13.
Adenosine cyclic 3′,5′-phosphoramidate was synthesized by reacting adenosine cyclic 3′,5′-phosphate with POCl3, in trimethyl phosphate for 1 h at O°C, followed by in situ treatment of the reaction mixture with a suspension of (NH4)2CO3 in anhydrous DMF or pyridine or DMF/pyridine mixture for 30 min at 25° C. Diastereoisomers (P)- and (P)- the relative quantities of which depended on the solvent of (NH4)2CO3 treatment, were separated by reversed phase partition chromatography. Hydrolysis of (RP)- and (SP)- proceeded with predominant (90% in 0.1 N HCl, 100% in 0.1 N NaOH) -P-O-C bond breaking. 相似文献
14.
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
15.
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
16.
Reaction of (2,3)-2,3-(cyclohexylidenedioxy)butanenitrile, derived from ethyl ()-lactate, with the magnesium enolate of t-butyl acetate gave the corresponding ()-β-amino acrylate derivative, which was transformed into N-benzoyl acosamine by acetylation, stereoselective hydrogenation, acidic hydrolysis, and ring-formation followed by reduction with diisobutylaluminium hydride. 相似文献
17.
Claudio Fuganti Piero Grasselli Paolo Casati Massimo Carmeno 《Tetrahedron letters》1985,26(1):101-104
Baker's yeast reduction of ethyl 4-azido- and 4-bromo-3-oxobutyrate affords (3) (8) and (3) (2), respectively, in high optical purity. 相似文献
18.
Lithiation of both ()- and ()-3-trimethylsilyl-2-propenyl ,-diisopropyl carbamate 2 affords the (2) -lithium compound 3. Aluminium- or titanium-mediated addition to aldehydes, 4 gives (1)-(3*4*)-enol carbamates 7. A stereospecific Peterson elimination (borontriflouride- or base-mediated) introduces the second double bond either with (3)- or with (3)-configuration. So just by reagent selection for each of the two steps, (1,3)-, (1,3)-, (1,3)-, or (1,3)- dienes 8 - 11, respectively, are prepared with stereoselectivities up to > 99.7% 相似文献
19.
Reduction of 5-benzoyl-8-methyl-2-oxo-3,4,4a,5,6,7-hexahydro-2H-pyrano[3,2-b] pyridine () with lithium aluminium hydride afforded (1R*,5S*,6R*,9S*)-2-benzyl-5-methyl-2-azabicyclo[3.3.1]nonane-6,9-diol (). 相似文献
20.
Tadashi Nakata Shigeto Nagao Sachiko Takao Tadasu Tanaka Takeshi Oishi 《Tetrahedron letters》1985,26(1):73-74
(1,3,5)-1,3-Dimethyl]-2,9-dioxabicyclo[3.3.1]nonane has been stereoselectively synthesized based on a highly stereoselective method for the synthesis of 1,3--polyol. 相似文献