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1.
Enamino-thiones 1 prepared from the corresponding enaminones by thiation with Lawesson's Reagent, were allowed to react with 2-chloroacrylonitrile and dimethyl acetylenedicarboxylate giving dihydro-2-thiopyrans, 2, and 4-thipyrans, 3, respectively. The reaction of 1a with ethyl propiolate at room temperature afforded 4-thipyrans, 4a, which on standing rearranged to 2-thiopyran, 5a(1, 3 amide shift). The reaction of 1b with ethyl propiolate produced 4b and 5b. Some of the 13C NMR data are reported. 相似文献
2.
The first asymmetric total synthesis of stoechospermol, a representative spatane diterpene having , , -tricyclo[5.3.0.02,6]decane ring system, was achieved. Using the intramolecular asymmetric (2+2) photocycloaddition reaction of the diastereomeric ester 11, the readily available butenolide 9 was transformed into the optically active dilactone 12a and 12b. Subsequent construction of tricyclic carbon ring system and introduction of substituents in a right stereochemistry gave rise to optically pure stoechospermol 1. 相似文献
3.
Dye-sensitized photooxidation of the imino-ether 5, prepared from yohimbine 1a, led to the α-amino nitrile 9a when the reaction was performed in the presence of oxygen and KCN. Derivative 9a was hydrolyzed to the amide 9b, the transformation of which to carboxamido-5β-yohimbine 15 was studied. 相似文献
4.
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
5.
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
6.
The ethylene acetals of and -acetoxyacetophenone 3a,b, prepared from the corresponding hydroxyacetophenones by treatment with acetic anhydride in pyridine and subsequently with ethylene glycol and -toluenesulphonic acid, give upon irradiation the expected photo-Fries products 4a,b (from 3a) or 6 (from 3b). These compounds are converted in part into diacetylphenols 5a,b as a consequence of a deacetalization, occurring to some extent during the irradiation and further in the chromatographic workup. The yields of the photoproducts and the / ratio (in the case of 3a) are very similar to those given in the literature for phenyl acetate. By contrast, the acetoxyacetophenones 2a,b do not undergo any appreciable change upon irradiation,showing the deactivating effect of the acetyl side chain. Therefore, it is concluded that cyclic acetals are suitable carbonyl blocking groups in order to circumvent the deactivating effect of acyl substituents on the photo-Fries rearrangement of aryl esters. 相似文献
7.
(η-Cyclopentadienyl)(triphenylphosphine)cobaltacyclopentadienes having an electron withdrawing substituent on the cyclopentadienyl ring, (η-C5H4R)(PPh3)(H) (1b: R = COOMe; 1c: R = COMe), were prepared in reasonable yields by treatment of a solution of (η-C5H4R)(PPh3)2Co with acetylene. A non-substituted cyclopentadienyl analog (1a: R = H) was also isolated in low yield according to a similar procedure. Novel dinuclear complexes were also formed as by-products and the structure of (η-C5H4R)Co(PPh2Me)Co(η-C5H4R) (2b: R = COOMe), having a μ2,η3-benzyl moiety, was determined by an X-ray crystallographic analysis. The X-ray analyses of 1a and 1b were also carried out. Crystals of 1a are monoclinic, space group Pa, a 8.529(3), b 16.010(6), c 8.028(4) Å, β 100.31(3)°, Z = 2; crystals of 1b are monoclinic, space group P21/a, a 8.327(2), b 36.468(7), c 8.021(1) Å, β 98.75(2)°, Z = 4; and crystals of 2b are monoclinic, space group P21/c, a 10.681(2), b 30.722(7), c 8.912(1) Å, β 93.55(1)°, Z = 4. They have been refined to R = 0.034, 0.047 and 0.050, respectively. 相似文献
8.
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
9.
M.T. Averbuch-Pouchot 《Journal of solid state chemistry》1982,41(3):262-265
The iodato-sulfate K4H2(S2I2O14) is monoclinic, with a unit cell: a = 13.84(1) Å, b = 7.173(5) Å, c = 7.443(5) Å, β = 93.16(1)°, and Z = 2. The crystal structure of this salt has been solved using 1956 independent reflections, with a final R value of 0.03. The main feature of this salt is the existence of a finite new heteropolyanion: (I2S2O14)?6. 相似文献
10.
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
11.
The cationic cyclization of the carbinol (Z) occurred stereoselectively and resulted in a mixture of the hydrindane and the octalin , both with configuration of side chain and angular methyl group. Cyclization of (E) yielded in and , both with -configuration. The structure of , was proved by transformation to the diketones ,. 相似文献
12.
4-Hydroxy cinnamic esters, thiolesters, aldehydes and alcohols, or related compounds, implied in the biosynthesis of lignins are easily synthesized in good yields from iminium salts of coumaric , ferulic and sinapic acids. No prior protection of the phenol group is needed in this method. 相似文献
13.
Reaction of the tricyclic epoxides () and () with boron trifluoride etherate leads to fluorohydrins () and () derived in the novel fluoride transfer, whereas () undergoes isomerization to spiro ketone (). 相似文献
14.
By an appropriate choice of cation, three of the four possible aldols from the reactions of the chiral α-silyloxy ketone 1 with aldehydes may be obtained. The , lithium enolate provides 6, the , boron enolate gives 7, and the magnesium enolate affords 8. 相似文献
15.
Herbert L. Holland David B. MacLean Russell G.A. Rodrigo Richard F.H. Manske 《Tetrahedron letters》1975,16(49):4323-4326
The reduction product of dehydrocordrastine, , with di-isobutylaluminum hydride spontaneously rearranged to the spirobenzylisoquinolines and , analogous to the alkaloids sibiricine (), corydaine (), and yenhusomidine (). 相似文献
16.
Cyclisation of readily available diary1-1,2 ethanes proceeds in SbF5,-HF at 0°C to yield tricyclic phenanthrenones , , and bearing an angular methyl group. This process implies the electrophilic attack of the more basic aromatic ring, reacting through its diprotonated form (on the oxygen and the meta carbon atom) on the second aromatic ring. Isomerization of these primary products may be observed to give ketones , , from and from ) and it has been demonstrated by the use of specifically deuterated that it involves stereospecific 1,2 hydride (or deuteride) shifts, without exchange. 相似文献
17.
《Tetrahedron: Asymmetry》1999,10(1):99-105
An alternative synthetic approach to diaryl ethers has been developed. In the key transformation, Robinson annulation of nonracemic aldehydes 16a,b, derived from l-glutamic acid 5-methyl ester and phenoxymethylvinyl ketone, provided α-phenoxyenones 17a,b. The Cbz-protected oxazolidine 17b was further converted into the diaryl ether 18b utilizing an oxidative selenation protocol. 相似文献
18.
The stereochemistry and product distribution resulting from reaction of 4',5',6',7'- tetrahydrospirol[cyclopropane-1,2']-[4,7]methano[2]indene(5), endo-2-methyl(6a) and 2,2-dunethyl-4,7-dihydro-4,7-methano-2-indene (6b), as well as 4',5',6',7'-tetrahydrospiro[cyclopentane-1,2']-[4,7]methano-[2]indene (7) with singlet oxygen have been determined. Stereochemical assignments to the diepoxide products were readily deduced by 13C-NMR comparison with the spectra of the parent isomcrs of established structure (X-ray). To unravel the stereochemistry of the epoxy aldehydes, recourse was made to 2D NOE experiments The observed stereosclectivity and reaction profile of each substrate are analyzed and placed in proper mechanistic and energetic perspective. 相似文献
19.
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
20.
11-Deoxyanthracyclinone precursors and have been prepared regiospecifically by the reaction of bromojuglone methyl ethers and with vinylketene acetal , prepared from the Hagemann's ester ketal . 相似文献