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1.
A complete reversal of diastereoselectivity was observed for reactions of the trifluoroacetaldehyde ethyl hemiacetal with enamines and imines, derived from propiophenones, that produce 4,4,4-trifluoro-1-aryl-3-hydroxy-2-methyl-1-butanones. This process serves as the first reliable, metal-free, complementary anti- and syn-selective method to prepare 4,4,4-trifluoro-1-aryl-3-hydroxy-2-methyl-1-butanones.  相似文献   

2.
Diimmonium salt 1 reacts with enamines 3 affording α-amino-pyrroles 4 . The synthetic potential of this reaction is discussed.  相似文献   

3.
By combining enamines, derived from aldehydes and diphenylprolinol trimethylsilyl ether (the Hayashi catalyst), with nitroethenes ((D6)benzene, 4‐Å molecular sieves, room temperature) intermediates of the corresponding catalytic Michael‐addition cycles were formed and characterized (IR, NMR, X‐ray analysis; Schemes 36 and Fig. 13). Besides cyclobutanes 2 , 1,2‐oxazine N‐oxide derivatives 3 – 6 and 8 have been identified for the first time, some of which are very stable compounds. It may not be a lack of reactivity (between the intermediate enamines and nitro olefins) that leads to failure of the catalytic reactions (Schemes 35) but the high stability of catalyst resting states. The central role zwitterions play in these processes is discussed (Schemes 1 and 2).  相似文献   

4.
Detailed herein is the photochemical organocatalytic enantioselective α‐alkylation of aldehydes with (phenylsulfonyl)alkyl iodides. The chemistry relies on the direct photoexcitation of enamines to trigger the formation of reactive carbon‐centered radicals from iodosulfones, while the ground‐state chiral enamines provide effective stereochemical control over the radical trapping process. The phenylsulfonyl moiety, acting as a redox auxiliary group, facilitates the generation of radicals. In addition, it can eventually be removed under mild reducing conditions to reveal methyl and benzyl groups.  相似文献   

5.
3-Aryl-1-phenyl-2-propen-1-ones Ia-f and aroylphenylacetylenes Va-d reacted under reflux for 3 hours with cyanoacetamide in the presence of sodium ethoxide to give the corresponding 4-aryl-3-cyano-6-phenyl-2-(1H)pyridones VI. However, when ketones Ia-e were refluxed with cyanoacetamide for one hour in the presence of sodium ethoxide or piperidine, they gave the corresponding 4-aryl-3-cyano-3,4-dihydro-6-phenyl-2-(1H)pyridones IIIa-e, which upon heating with selenium gave the corresponding 2-pyridones VI. The structures of the products are based on chemical and spectroscopic evidence.  相似文献   

6.
5-Amino-2,3,6,7-tetrahydrothiocines were reacted with arylazides yielding 1-aryl-9a-amino-1,3a,4,5,7,8,9,9a-octahydrothiocino[4,5-d]-1,2,3-triazoles which could be deaminated to 1-aryl-1,4,5,7,8,9-hexahydrothiocino-[4,5-d]-1,2,3-triazoles. Similarly, the above enamines yielded, with nitrile oxides, 3-aryl-9a-amino-3a,4,5,8,9,9a-hexahydrothiocino[4,5-d]isoxazoles which were transformed with acids into 3-aril-4,5,8,9-tetrahydrothiocino-[4,5-d]isoxazoles.  相似文献   

7.
The asymmetric conjugate addition of malonate esters to α,β‐unsaturated N‐sulfonyl imines is catalyzed by PyBOX/La(OTf)3 complexes in the presence of 4 Å MS. The reaction gives the corresponding E enamines bearing a stereogenic center at the allylic position with good yields and enantiomeric ratios up to 97:3. This reaction provides a synthetic entry to chiral δ‐aminoesters and piperidones.  相似文献   

8.
Reactions with derivatives of γ-chloroacetoacetic acid Ethyl γ-chloroacetoacetate reacts with ammonia to give ethyl β-amino-γ-chloro-crotonate; with aniline, however, β-anilino-crotonic acid γ-lactone is formed. The reaction of ethyl α-cyano-γ-chloro-acetoacetate with arylamines yields 1-aryl-2-amino-3-ethoxycarbonyl-pyrrolin-4-ones.  相似文献   

9.
A series of 2‐amino‐7‐methoxy‐4‐aryl‐4H‐chromene‐3‐carbonitrile compounds 2 were obtained by condensation of 3‐methoxyphenol with β‐dicyanostyrenes 1 in absolute ethanol containing piperidine. The intermediate enamines 3 were prepared by compounds 2 with 5‐substituted‐1,3‐cyclohexanedione using p‐toluenesuflonic acid (TsOH) as catalyst. The title compounds 11‐amino‐3‐methoxy‐8‐substituted‐12‐aryl‐8,9‐dihydro‐7H‐chromeno[2,3‐b]quinolin‐10(12H)‐one 4 were synthesized by cyclization of the intermediate enamines 3 in THF with K2CO3 /Cu2Cl2 as catalyst. The structures of all compounds were characterized by elemental analysis, IR, MS, and 1H NMR spectra. The crystal structure of compound 4i was determined by single‐crystal X‐ray diffraction analysis.  相似文献   

10.
The pyrazolo[1,5‐a]pyrimidines 4, 10, 11 and 14 were synthesized from reaction of 4‐aryazo‐2,5‐diaminopyrazoles 1 with cyclic β‐ketoesters 2a,b or cyclic β‐ketoesters 7, 8 or acetoacetanilide 12 , respectively. The reaction of 1 with the enamines 15, 16 and 17 yielded also the pyrazolo[1,5‐a]pyrimidines 18, 20 and 21 , respectively.  相似文献   

11.
2-Hydroxymethyl-5-methoxy-4-H-pyran-4-one ( 1 ) reacts with aniline and six aniline derivatives in very dilute aqueous hydrochloric acid at reflux temperature to give the N-aryl-γ-pyridone. A second procedure utilizes the aromatic amine hydrochloride by reacting it with 1 in aqueous medium at reflux temperature. p-Nitroaniline hydrochloride and 1 give the N-aryl-γ-pyridone in 65% yield, as opposed to 12% from the dilute acid procedure.  相似文献   

12.
By the promotion of chlorotrimethylsilane, asymmetric Michael reaction of the chiral enamines (2) of α-alkyl β-keto esters (1) with methyl vinyl ketone and ethyl acrylate proceeded to afford, after hydrolysis, either enantiomer of the corresponding adducts (4) in a good enantioselectivity.  相似文献   

13.
A combined experimental and theoretical study is presented on 2-azetines, a class of azaheterocyclic compounds, which are difficult to access but have shown a unique reactivity as strained cyclic enamines. New highly substituted 2-azetines bearing aryl substituents at the 2- and 4-position were synthesized from 3,3-dichloroazetidines. Whereas 2-aryl-3,3-dichloroazetidines gave stable 2-aryl-3-chloro-2-azetines upon treatment with sodium hydride in DMSO, 2,4-diaryl-3,3-dichloroazetidines showed a remarkably different reactivity in that they afforded benzimidoyl-substituted alkynes under similar mild treatment with base. The formation of the alkynes involves electrocyclic ring opening of intermediate 2,4-diaryl-3-chloro-2-azetines and elimination of hydrogen chloride. Ab initio theoretical calculations confirmed the experimental findings and demonstrated that the 4-aryl substituent is responsible for this remarkably enhanced reactivity of 2-azetines toward electrocyclic conrotatory ring opening by a significant decrease in reaction barrier of about 30 kJ/mol. This activation effect by an aryl group in the allylic position toward electrocyclic ring opening of unsaturated four-membered rings is of general importance since a similar increased reactivity of 4-aryloxetes, 4-arylthiete-1,1-dioxides, and 3-arylcyclobutenes has been reported in literature as well.  相似文献   

14.
ω-Cyanoacetophenone (1a) and its derivatives 1b-c react with morpholine (or piperidine) to give mainly 2,4-diaryl-3-eyano-6-morpholino- (or piperidino-) pyridine derivatives (5) ; relative β-aminoeinnamonitriles 6 and very small amounts of amidines 4 are also obtained. When pyrrolidine is used compounds 5 cannot be detected and enamines 6 are the main product. A mechanism involving the intermediate formation of enamines 6 (as electrophiles) and of carbanions 11 (as nucleophiles) is proposed to explain this new synthesis of aminopyridine derivatives.  相似文献   

15.
The reaction of malononitrile with α-phenylcinnamonitriles in ethanolic sodium ethanethiolate is studied as a convenient route to 2-amino-4-aryl-5-cyano-6-ethylthio-3-phenyl-3,4-dihydropyridines ( 5 ) and the corresponding pyridines 6 . From the study of the structure of 5a (Ar = Ph) we can conclude that this cyclization reaction proceeds via a site-selective addition of the ethanethiolate to the cyano group i of the 1,3-tricarbonitrile ( 2 ).  相似文献   

16.
Condensation of 1H-indole-3-ethanamines 1 with cyclic β-keto esters 2 under azeotropic conditions followed by acid-catalyzed ring closure of the resulting enamines 3 gave 2′,3′,4′,9′-tetrahydrospiro[piperidine-3,1′,-[1H]pyrido[3,4-b]indole] -4-carboxylic acid alkyl esters 4 . Condensation of 1 with 2-acylcycloalkanones 8 gave two types of enamines, 10 and 11 , respectively. Enamines 10 on treatment with acid gave 1-(2′,3′,4′,9′-tetrahydro-3H-pyrido[3,4-b]indol-1-yl)-1-alkylcyclohexanols 17 . Compounds 17 were further dehydrated to give cycloalkane derivatives 19.  相似文献   

17.
The reaction of sulfene with 3-dialkylaminomethylene-4-chromanone and 3-dialkylamino-methylene-6-methyl-4-ehromanone gave 1,4-cycloadducts which are derivatives of a new heterocyclic system, i.e., 5H-1,2-oxathiino[5,6-c][1]benzopyran. The structures of the adductswere determined by ir and nmr spectral data. Two new α-hydroxymethyleneketones (3-hydroxy-methylene-4-chromanone and its 6-methyl analogue) as well as some of their derived enamines were prepared. During the preparation of N,N-diethylenamines a self-condensation occurs, which gives the byproducts Xa-b.  相似文献   

18.
A novel synthetic approach towards α-trifluoromethyl-phenethylamines was elaborated by reduction of the electron deficient β-aryl-α-trifluoromethyl enamines and imines with sodium cyanoborohydride in the presence of trifluoroacetic acid. The starting imines were prepared by the reaction of primary amines with β-aryl-α-trifluoromethyl enamines or β-chloro-β-(trifluoromethyl)styrenes.  相似文献   

19.
Reactions of N-phenyl-3-oxobutanethioamide with 3-aryl-2-propenoyl chlorides in acetone in the presence of potassium carbonate give rise to 4-aryl-5-acetyl-1-phenyl-6-thioxopiperidin-2-ones, 2-aryl-5-acetyl-6-phenylamino-2,3-dihydro-4H-thiopyran-4-ones, and 6-aryl-2-acetonylidene-3-phenyl-5,6-dihydro-4H-1,3-thiazin-4-ones whose structure was proved both by spectral methods and chemical transformations.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 292–296.Original Russian Text Copyright © 2005 by Britsun, Borisevich, Samoilenko, Lozinskii.  相似文献   

20.
《Mendeleev Communications》2022,32(4):449-451
One-pot synthesis of cyclopentane-fused 5'-aryl-4- cycloalkylamino-2,2'-bipyridines based on the neat (200 °C) reaction of 3-(4-bromopyridin-2-yl)-1,2,4-triazines with enamines is reported. In the course of the transformation, consecutive aza-Diels–Alder reaction and nucleophilic substitution of bromine atom under the action of the liberating amine occur. The possibility of the solvent- and catalyst-free replacement of 4-positioned bromine atom in 2,2'-bipyridines by amino moieties was demonstrated.  相似文献   

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