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1.
A highly regioselective method for the synthesis of 3, 4-disubstituted 1H-pyrroles has been developed employing the ipso-directing property of a trimethylsilyl group. As a key starting material in this study, the known 3,4-bis(trimethylsilyl)-1H-pyrrole (3), was protected with carefully chosen groups, namely tert-butoxycarbonyl, N,N-dimethylaminosulfonyl, p-toluenesulfonyl, and triisopropylsilyl. A highly regioselective monoiodination of these 1-protected pyrroles was achieved by reaction with iodine-silver trifluoroacetate at low temperatures. Subsequent palladium-catalyzed cross-coupling reactions afforded 1-protected-4-substituted 3-trimethylsilyl-1H-pyrroles, which again underwent further room-temperature ipso-iodination and palladium-catalyzed cross-coupling reactions to provide symmetrical and unsymmetrical 1-protected-3,4-disubstituted 1H-pyrroles. Deprotection of 1-(tert-butoxycarbonyl) and 1-(N, N-dimethylaminosulfonyl) groups was found to be nontrivial. The 1-(p-toluenesulfonyl) protecting group was eventually proved to be superior to other protection groups, because it was readily removed after stepwise ipso monoiodinations and palladium-catalyzed cross-coupling reactions.  相似文献   

2.
合成α 酮酸的新方法   总被引:1,自引:0,他引:1  
本文报道了一种新的简便的合成α-酮酸(4)的新方法. 用三氟乙酸酐在4-N,N-二甲基氨基吡啶催化下在二氯乙烷溶剂中和易于制得的2,3-二(三甲基硅氧基)羧酸三甲基硅酯(1)反应生成2,3-二(三氟乙酰羧酸三甲硅酯(2). 向反应混合物中加入吡啶生成2-三氟乙酰氧基-2-烯酸(3). 分别用氢氧化钾水溶液和盐酸处理3得产物4 .  相似文献   

3.
A stereoselective total synthesis of (S)-Virol C and (S)-1-dehydroxyvirol A has been developed, based upon the selective and sequential substitution of the two trimethylsilyl groups of readily available 1,4-bis(trimethylsilyl)-1,3-butadiyne.  相似文献   

4.
Herein, we provide a new protocol to reduce various transition-metal complexes by using organosilicon compounds in a salt-free fashion with the great advantage of generating pure low-valent metal species and metallic(0) nanoparticles, in sharp contrast to reductant-derived salt contaminants obtained by reduction with metal reductants. The organosilicon derivatives 1,4-bis(trimethylsilyl)-2,5-cyclohexadiene ( 1 a ), 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene ( 1 b ), 1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene ( 2 a ), 2,5-dimethyl-1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene ( 2 b ), 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene ( 2 c ), and 1,1′-bis(trimethylsilyl)-1H,1′H-4,4′-bipyridinylidene ( 3 ) all served as versatile reductants for early transition-metal complexes and produced only easy-to-remove organic compounds, such as trimethylsilylated compounds and the corresponding aromatics, for example, benzene, toluene, pyrazine, and 4,4′-bipyridyl, as the byproducts. The high solubility of the reductants in organic solvents enabled us to monitor the catalytic reactions directly and to detect any catalytically active species so that we could elucidate the reaction mechanism.  相似文献   

5.
Oligomerization of vinyl- and ethyl-trimethylsilanes in the presence of homogeneous nickel, cobalt and titanium catalytic systems has been studied. Vinyl-trimethylsilane forms linear dimeric products, 1,4-bis(trimethylsilyl)butenes. Using the titanium catalytic system, in addition to butenyldisilane, a branched dimeric product, 1,3-bis(trimethylsilyl)-3-methylprop-1-ene, and a linear trimer 1,3,6-tris(trimethylsilyl)hex-3-ene are formed. Ethynyltrimethylsilane, in the presence of the nickel catalytic system, is converted into a linear dimer, 1,4-bis(trimethylsilyl)but-3-ene-1-yne, and linear trimer, 1,4,6-tris(trimethylsilyl)hex-3,5-diene-1-yne.  相似文献   

6.
Treatment of 1,3-dienes and 1,3,5-cycloheptatriene by chlorotrimethylsilane in the presence of wire of lithium led mainly to reductive dimerization with formation of bis(allylsilane) derivatives. Bis-silyl compounds obtained: from 1,3-butadiene, 1,8-bis(trimethylsilyl)-2,6-octadiene (70%); from isoprene, (Z,Z)-2,7-dimethyl-1,8-bis(trimethylsilyl)-2,6-octadiene (44%) and 2,6-dimethyl-1,8-bis(trimethylsilyl)-2,6-octadiene (19%); from butadiene-isoprene mixture (1:1), 3-methyl-1,8-bis(trimethylsilyl)-2,6-octadiene (55%); from 2,3-dimethylbutadiene, (E,E)-2,3,6,7-tetramethyl-1,8-bis(trimethylsilyl)-2,6-octadiene (36%), from 1,3-cyclohexadiene, 4,4′-bis(trimethylsilyl)-bicyclohexyl-2,2′-diene (48%); from 1,3,5-cycloheptatriene, 1,1′-bi[(S,S)-6-(trimethylsilyl)cyclohepta-2,4-dien-1-yl] (53%). The structure of the various intermediates (radical anion, dianion, silylated radical, silylated anion) has been established by calculations at the B3LYP/6-311++G(d,p) level of theory with zero-point energy correction. These results are in accordance with a pathway including the formation of a radical anion, its silylation furnishing to a γ-silylated allylic radical followed by a dimerization reaction in the head to head manner.  相似文献   

7.
[reaction: see text] Copper-mediated homocoupling of sterically hindered 2-(2,4,6-tri-tert-butylphenyl)-1-trialkylsilyl-2-phosphaethenyllithiums afforded 1,2-bis(trialkylsilyl)-3,4-diphosphacyclobutenes (1,2-dihydrodiphosphetenes) through a formal electrocyclic [2+2] cyclization in the P=C-C=P skeleton as well as 2-trimethylsilyl-1,4-diphosphabuta-1,3-diene. Reduction of 1,2-bis(trimethylsilyl)-3,4-diphosphacyclobutenes followed by quenching with electrophiles afforded ring-opened products, (E)-1,2-bis(phosphino)-1,2-bis(trimethylsilyl)ethene and (Z)-2,3-bis(trimethylsilyl)-1,4-diphosphabut-1-ene. The structures of the ring-opened products indicated E/Z isomerization around the C=C bond after P-P bond cleavage of 5, and the isomerization of the P-C=C skeleton. Ring opening of 1,2-bis(trimethylsilyl)-3,4-diphosphacyclobutenes affording (E,E)- and (Z,Z)-1,4-diphosphabuta-1,3-dienes was observed upon desilylation.  相似文献   

8.
Under the agency of the potent lithiating agent, n-butyllithium in TMEDA, an array of organosilanes was found to undergo 1, n-silyl rearrangements via carbanionic intermediates. Unambiguous 1, 2-, 1, 3- and 1, 4-silyl shifts were uncovered in 1-trimethylsilyl-1, 1, 2-triphenylethane, 1, 1-bis(trimethylsilyl)-1-phenylalkanes and 1, 2-bis(trimethylsilyl)-1, 2-diphenylethane, respectively. Cross-over and competition experiments established that these rearrangements generally are intramolecular and occur with decreasing ease in the order, 1, 2 > 1, 3 > 1, 4. In other compounds, such as 1, 1-bis(trimethylsilyl)-1, 2-diphenylethane, 1, n-bis(trimethylsilyl)benzenes and triphenyl(trimethylsilyl)methane, competing 1, n-silyl shifts occurred. Attack of the organolithium intermediates on solvent and silicon—lithium exchange were significant side reactions in some instances. 1-Trimethylgermyl-1, 1, 2-triphenylgermane underwent no discernible rearrangement but rather gave the product expected from germanium—lithium exchange. By conducting time and competition studies, it was shown that lithiation is the product-determining step in these rearrangements and that dual pathways, namely 1, 3-versus consecutive 1, 2- 1, 4-pathways, are operative in certain rearrangements.  相似文献   

9.
Synthesis of new imines and amines containing organosilicon groups   总被引:1,自引:0,他引:1  
The Peterson olefination reaction of terephthalaldehyde with tris(trimethylsilyl)methyl lithium, (Me3Si)3CLi, in THF at 0 °C gives 4-[2,2-bis(trimethylsilyl)ethenyl]benzaldehyde (1) and 4,4-bis[2,2-bis(trimethylsilyl)ethenyl]benzene (2). The new aldehyde (1) reacts with variety of amines in ethanol to afford the corresponding imines (3) containing vinylbis(trimethylsilyl) group. The newly synthesized imines (3) can be completely converted into amines containing vinylbis(trimethylsilyl) group with an excess amount of NaBH4. In the case of N-[4-(2,2-bis(trimethylsilyl)ethenyl)benzyl]-2,6-dimethylaniline LiAlH4 was used as a reducing agent in THF.  相似文献   

10.
A reaction of sodium bis(trimethylsilyl)amide with 2-bromopyridine leads to N,N-bis(trimethylsilyl)- and N,3-bis(trimethylsilyl)-2-pyridinamine.  相似文献   

11.
The thermolysis of 1-mesityl-3-phenyl-1,2-bis(trimethylsilyl)-1-silacyclopropene at 280°C afforded 1-mesityl-3,3-dimethyl-4-phenyl-5-(trimethylsilyl)-1,3-disilacyclo-4-pentene and 1-mesityl-1,3-bis(trimethylsily)-1-silaindene. Similar thermolysis of 2-mesityl-2-(phenylethynel)hexamethyltrisilane produced the same products.  相似文献   

12.
A practical and general synthetic approach to a series of 4-aryl-but-3-en-1-ynes is described. In the presence of palladium complexes a variety of aryl bromides (or iodides) undergo coupling with two equivalents of trimethylsilylacetylene with the formation of (E)-4-aryl-1,3-bis(trimethylsilyl)but-3-en-1-ynes. The protocol is simple, efficient, and affords synthesis of regio- and stereoselectively target products in good to high yields.  相似文献   

13.
An efficient synthetic approach to a variety of unsymmetrically substituted conjugated diynes has been developed, starting from the readily available 1,4-bis(trimethylsilyl)-1,3-butadiyne, based upon the selective and sequential substitution of the trimethylsilyl groups with alkyl, aryl and vinyl groups.  相似文献   

14.
Tris[4-(substituted)furan-3-yl]boroxines 2 , prepared from the corresponding 4-(substituted)-3-(trimethylsilyl) furan 1, were converted successfully to 4-(substituted)-3-(tributylstannyl)furans 3 through palladium-catalyzed cross-coupling reactions with tributylstannyl chloride. Palladium-catalyzed cross-coupling reactions of 3 with organohalides afforded 3,4-disubstituted furans 4 . Regiospecific iodination of 4-(trimethylsilyl)-3-((tributylstannyl) furan ( 3a ) gave 4-iodo-3-(trimethylsilyl)furan ( 5 ), which reacted with excess ethyl acrylate under a common Heck-condition to produce 2,3-bis(trans-ethoxycarbonylvinyl)-4-(trimethylsilyl)furan ( 6 ). A thermal 6-electrocyclic reaction followed by dehydration converted 6 into benzo[2,3-6]furan 8 . Oxidation of 2 generated the corresponding 4-substituted-3(2H)-furanones 9 .  相似文献   

15.
A new class of dithiostannanes and dithiogermanes have been prepared from 1,1'-binaphthyl-2,2'-dithiol and 3,3'-bis(trimethylsilyl)-1,1'-binaphtho-2,2'-dithiol. While reduction of 4-butyl-4-chloro-3,5-dithia-4-stanna-cyclohepta[2,1-a;3,4-a']dinaphthalene to the corresponding tin hydride was unsuccessful, 4-tert-butyl-3,5-dithia-4-germa-cyclohepta[2,1-a;3,4-a']dinaphthalene and 4-tert-butyl-2,6-bis(trimethylsilyl)-3,5-dithia-4-germa-cyclohepta[2,1-a;3,4-a']dinaphthalene were obtained by reduction of the parent germanium chlorides with NaBH(4) and LiBH(4), respectively. Kinetic constants for hydrogen transfer to a primary alkyl radical were measured for both germanium hydrides. Reduction of alpha-halo carbonyl compounds by these germanium hydrides occurs with moderate ee values (up to 42%), while hydrogermylation of methyl methacrylate occurs with low selectivity (<3/1) for the former hydride but high selectivity (>10/1) for the latter.  相似文献   

16.
Spin trapping of superoxide by diester-nitrones   总被引:1,自引:0,他引:1  
The nitrone N-[(1-oxidopyridin-1-ium-4-yl)-methylidene]-1,1-bis(ethoxycarbonyl)ethylamine N-oxide (DEEPyON) was synthesized and used as a spin trapping agent. The kinetic aspects of the superoxide detection by this new spin trap and by two other diester-nitrones, i.e. 2,2-diethoxycarbonyl-3,4-dihydro-2H-pyrrole-1-oxide (DEPO) and N-benzylidene-1,1-bis(ethoxycarbonyl)ethylamine N-oxide (DEEPN), were examined by determining the rate constants for the trapping reaction and for the spin adduct decay at pH 7.2. Comparing the results obtained to those given by analogous monoester-nitrones showed that both the spin trapping and the adduct decay reactions were faster in the presence of a second ester group in the cyclic nitrone series, while the superoxide trapping capacities of linear diester-nitrones were found to be dramatically weak. It follows from this study that DEPO and 2-ethoxycarbonyl-2-methyl-3,4-dihydro-2H-pyrrole-1-oxide (EMPO) are superior when it comes to superoxide detection. Below 0.005 mol dm(-3), DEPO is to date the only nitrone capable of clearly detecting superoxide, while EMPO should be preferred at higher spin trap concentration.  相似文献   

17.
Several new 1,1-disubstituted siloles containing substituents on the ring carbon atoms have been synthesized. The new siloles: 1,1-dihydrido-2,5-bis(trimethylsilyl)-3,4-diphenylsilole (5), 1,1-dihydrido-2,5-dimethyl-3,4-diphenylsilole (6), 1,1-dimethoxy-2,5-bis(trimethylsilyl)-3,4-diphenylsilole (7), 1,1-bis(4-methoxyphenyl)-2,5-bis(trimethylsilyl)-3,4-diphenylsilole (8), 1,1-dipropoxy-2,5-bis(trimethylsilyl)-3,4-diphenylsilole (9), and 1,1-dibromo-2,5-bis(trimethylsilyl)-3,4-diphenylsilole (13) were prepared from reactions originating from the previously reported, 1,1-bis(diethylamino)-2,5-bis(trimethylsilyl)-3,4-diphenylsilole (1) or 1,1-bis(diethylamino)-2,5-dimethyl-3,4-diphenylsilole (2). In addition, three other new organosilane byproducts were observed and isolated during the current study, bis(4-methoxyphenyl)bis(phenylethynyl)silane (11), bis(4-methoxyphenyl)di(propoxy)silane (12) and 1-bromo-4-bromodi(methoxy)silyl-1,4-bis(trimethylsilyl)-3,4-diphenyl-1,3-butadiene (14). Compounds 13 and 14 were characterized by X-ray crystallography and 14 is the first 1,1-dibromosilole whose solid state structure has been determined.  相似文献   

18.
4,4′-Bis[2-(2-phenylethynyl)-3-thienyl]biphenyl, 4,4′-bis[2-{2-(trimethylsilyl)ethynyl}-3-thienyl]biphenyl and their congeners were prepared and their properties were studied. Extension of π-system through the central benzene ring was suggested by UV-vis spectra. Connection of two 1,4-bis[2-{2-(trimethylsilyl)ethynyl}-3-thienyl]benzene units was exemplified.  相似文献   

19.
The coordination chemistry of 2,5-dicarbothioamidopyrrole ligands, namely N2,N5-dibutyl-3,4-diphenyl-1H-pyrrole-2,5-bis(carbothioamide) and N2,N5,3,4-tetraphenyl-1H-pyrrole-2,5-bis(carbothioamide), has been investigated with Cu(II) metal centres by means of X-ray crystallography. This resulted in the formation of the expected planar S,N,S' coordinated complex for the former ligand and unexpected ring-closure reactions, with formation of benzothiazole sidearms, for the latter. Both Cu(II) and Cu(I), used in large excess, were found to favour the ring-closure reaction, although the structural characterisation of the resulting complexes contained only Cu(II) cations, with varying coordination geometries ranging from square planar and square-based pyramidal to tetrahedral. By repeating the reaction using a slight excess of Cu(II) (2?:?1) two more different structures were obtained where the metal was coordinated to the original ligand, N2,N5,3,4-tetraphenyl-1H-pyrrole-2,5-bis(carbothioamide), or to the mixed ligand where only one of the thioamide substituents had converted to a benzothiazole. The essential role of Cu for the ring closure reaction was also established by comparing its complex with structural features of the analogous Co(II) complex, the latter revealing no ring closure to give benzothiazole substituents and co-crystallisation of a mixed Co(II)/Co(III) complex. Finally, the structure and photophysical properties of the corresponding 3,4-diphenyl-2,5-bis(benzothiozol-5-yl)-pyrrole ligand, obtained via treatment of the thioamide with K(3)[Fe(CN)(6)], were also investigated revealing a blue-centered emission.  相似文献   

20.
Tetrakis(trimethylsilyl)ethylene (1), tris(trimethylsilyl) (dimethylsilyl)ethylene and 1,2-bis(trimethylsilyl)-1,2-bis(dimethylsilyl)ethylene have been prepared and spectral properties are described. ESR spectra of anion and cation radicals of 1 are also recorded, indicating a nonplanar twisted structure for 1. These crowded olefins show interesting reversible thermochromism.  相似文献   

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