共查询到20条相似文献,搜索用时 0 毫秒
1.
Deb K. Barma Anish Bandyopadhyay Bhavani Sangras Charles Mioskowski J.R. Falck 《Tetrahedron letters》2004,45(30):5917-5920
CrCl2-induced olefination of aldehydes using methyl dichloroacetate exclusively generates (E)-α,β-unsaturated esters in excellent yields. The intermediate α-chloro-β-hydroxy adducts could also be isolated in good yields under conditions of limited reagent. 相似文献
2.
Federico Tutino 《Tetrahedron》2009,65(11):2372-2376
(Z)-Axinohydantoin and (Z)-debromoaxinohydantoin, two pyrrole-imidazole alkaloids isolated from different marine sponges, possess moderate activities in inhibiting the progress of the cell cycle at different phases. A stereoselective synthesis of both natural products was achieved. The key step in the synthetic pathway was the installation of the hydantoin northern ring by using 1-benzoyl-2-methylsulfanyl-1,5-dihydroimidazol-4-one. 相似文献
3.
The CrCl2-mediated two-carbon halo-homologation of aryl, alkenyl, and aliphatic aldehydes with chloral ethyl hemiacetal or bromal affords (Z)-α-chloro- and (Z)-α-bromo-α,β-unsaturated aldehydes, respectively, in good to excellent yields and high stereoselectivity. The utility of this methodology was illustrated by a synthesis of 2-chloropentadec-2(Z)-enal, a toxin isolated from the marine red alga Laurencia flexilis. 相似文献
4.
Methyl (Z)-α-methoxyacrylates are generated in good yields by a mild, stereospecific two-carbon homologation of a wide variety of aldehydes utilizing commercial methyl 2,2-dichloro-2-methoxyacetate and CrCl2 under Barbier conditions at room temperature. A rational mechanism based upon a Reformatsky-type addition pathway or an in situ generated (E)-trioxo-chromium vinylidene carbenoid is proposed. 相似文献
5.
Masanori Yoshida 《Tetrahedron》2006,62(36):8636-8645
Stereoselective synthesis of fluoroalkenes is described. (Z)-2-Fluoro-1-alkenyl(phenyl)iodonium tetrafluoroborates (1) were synthesized stereoselectively in good yields by Michael-type addition of HF to 1-alkynyl(phenyl)iodonium tetrafluoroborates (2) with a commercially available HF reagent, hydrofluoric acid or Et3N-3HF. Pd-catalyzed cross-coupling reactions using 1 gave (Z)-2-fluoro-1-alkene derivatives in moderate yields. The treatment of 1 with KI in the presence of a catalytic amount of CuI gave (Z)-2-fluoro-1-iodo-1-alkenes (3). Pd-catalyzed cross-coupling reactions of 3 gave better results than that of 1, and a variety of (Z)-2-fluoro-1-alkene derivatives were synthesized in good yields. 相似文献
6.
Pd-catalyzed cross-coupling reaction of (E)-bromoenyne 1Z with 1-alkyne and tributylvinyl-stannane occurs with retention of the configuration in benzene but with an inversion of the configuration in DMF or CH2Cl2. On the other hand, that of (Z)-bromoenyne 1E occurs with retention of the configuration in these solvents. 相似文献
7.
Claudio C. Silveira Rodrigo Cella Adriano S. Vieira 《Journal of organometallic chemistry》2006,691(26):5861-5866
Alkyne-titanium complexes 3, readily prepared in situ by the reaction of alkynes with Ti(O-i-Pr)4/2 i-PrMgCl, react with electrophilic chalcogen species under mild conditions to provide the corresponding addition products in fair to good yields. The obtained vinylic vic-bis(arylchalcogenides) 4 are useful synthetic intermediates for introducing vinyl functions into organic molecules. 相似文献
8.
A Ni-catalyzed cross-coupling reaction of (Z)-5-(tert-butyldiphenylsilyl)oxy-3-bromo-1-trimethylsilyl-3-penten-1-yne (1) with alkyl Grignard reagent gives (Z)-3-alkyl-5-(tert-butyldiphenylsilyl)oxy-1-trimethylsilyl-3-penten-1-ynes (2) stereospecifically in good yields. The (Z)-enyne 2a is transformed in four steps to (Z)-3-methyl-5-silyloxy-3-pentenal (3), which is coupled with ketophosphonate 4 to give enone 13. The η-hydroxyallyl methanesulfonate derived from 13 is cyclized to 3,6-dihydro[2H]pyran by an intramolecular SN2′ reaction stereoselectively, furnishing a C17-C27 carbon unit of (−)-laulimalide. 相似文献
9.
Masanori Yoshida 《Journal of fluorine chemistry》2004,125(4):527-529
(Z)-β-Fluoro-α,β-unsaturated esters were stereoselectively synthesized from (Z)-2-fluoro-1-alkenyliodonium salts by the Pd-catalyzed methoxycarbonylation reaction. The reaction proceeded at room temperature and various functional groups on the substrate can tolerate the reaction conditions. 相似文献
10.
Treatment of trisubstituted (Z)-bromoalkenyl-pinacolboronates with terminal alkynes in the presence of cuprous iodide, palladium(0) tetrakis(triphenylphosphine) and Hünig’s base leads to the formation of 1,2,4,6-tetrasubstituted aromatic compounds in a one-pot fashion. Substrate scope was shown for three trisubstituted (Z)-bromoalkenyl-pinacolboronates and four terminal alkynes. 相似文献
11.
[reaction: see text]. A highly flexible and stereoselective protocol for the synthesis of branched (E)- and (Z)-trisubstituted alkenes has been developed. The key steps are hydrozirconation-iodination of (1-alkynyl)trimethylsilane followed by Negishi-type cross-coupling. The resultant (Z)-vinyl silane is iododesilylated and subjected to a second cross-coupling reaction to give the trisubstituted olefin. Model studies aimed at the construction of the C14-C15 (Z)-trisubstituted olefin of discodermolide and the C8-C9 (Z)-trisubstituted olefin of callystatin A and analogues are also described. 相似文献
12.
Pentacarbonyl(η2-cis-cyclooctene)chromium(0) (1) catalyzes efficiently reactions of diazo compounds with electron-rich furans. The reaction of 2-methoxyfuran (2) with alkyl α-diazoarylacetate (3a-g) furnishes the (2E,4Z)-2-aryl-hexadienedioic acid diesters (4a-g) in excellent yields. These reactions are highly regioselective. The cyclopropanation intermediates formed from 1 and diazo compounds 3a-g always arise from a carbene addition to the less substituted CC bond of 2. The resulting cyclopropanation product undergoes a ring opening reaction to form the corresponding (2E,4Z)-2-aryl-hexadienedioic acid diesters (4a-g). The pentacarbonylchromium(0)-catalyzed reactions of 2-alkylfuran (5a-b) with ethyl α-diazophenylacetate (3a) and 9-diazo-9H-fluorene (3h) produce the 1(E),3(E)-butadienes (6a-d) in very good yields. 相似文献
13.
Muga Nakagawa 《Tetrahedron letters》2005,46(32):5257-5261
Reactions of 2,2-dibromo-2-fluoroethyl alkyl ethers and dibromofluoromethylcarbinyl silyl ethers with CrCl2 and Mn powder provided 2-fluorovinyl alkyl ethers and 1-fluoro-2-alkenyl enol silyl ethers in high yields and in Z selective manner. 相似文献
14.
Randolf D Köhn David Smith Martina Prinz Gabriele Kociok-Köhn 《Journal of organometallic chemistry》2003,683(1):200-208
Complexes of N-substituted 1,3,5-triazacyclohexanes with CrCl3 form 1:1 adducts with [PhNMe2H][B(C6F5)4] with increased solubility in toluene. Addition of AliBu3 leads to free PhNMe2 and a complex with [B(C6F5)4]− weakly coordinated to chromium via a meta-fluorine atom. This complex can polymerise and/or trimerise olefins similar to methyl aluminoxane activated complexes. Decomposition of the active complex involves transfer of the triazacyclohexane to aluminium leading to [(triazacyclohexane)AliBu2][B(C6F5)4] and [(arene)2Cr][B(C6F5)4]. These chromium(I) complexes have been characterised by X-ray crystallography and prove that chromium is reduced to the oxidation state +I during the catalysis. 相似文献
15.
Zhichao Ma 《Tetrahedron》2008,64(27):6500-6509
A Na2S2O4-promoted radical addition reaction of perfluoroalkyl iodides with allenes has been studied in which a Z/E mixture of 2-iodo-1-perfluoroalkyl-2-alkenes 3 were afforded in 52-69% yields. A kinetic resolution using Sonogashira coupling reaction in MeCN using Et2NH as the base was developed to synthesize the 2-iodo-1-perfluoroalkyl-2(Z)-alkenes (Z-3) and E-4-perfluoroalkylmethylalk-4-en-2-ynols (E-5) stereoselectively. A complete Sonogashira coupling procedure in Et2NH at 40 °C was also developed affording a mixture of E and Z-4-perfluoroalkylmethyl-4-en-2-ynols (E-5 and Z-5), which may be easily separated by chromatography on silica gel. 相似文献
16.
A simple preparation of trisubstituted alkenes by condensation of β-diketones or β-ketoesters with aldehydes in presence of NbCl5 as a Lewis acid catalyst in solvent-free conditions is described. 相似文献
17.
(Z)-γ-Cyano-β-perfluoroalkyl-β,γ-unsaturated esters have been synthesized by the reaction of perfluoroacylated phosphonates with organozinc reagent in 50-71% (three steps) yields. 相似文献
18.
Giuseppe Bartoli Sandra Giuli Enrico Marcantoni Massimo Massaccesi 《Tetrahedron letters》2006,47(37):6501-6504
The arylidene malonates with two different geminal carboxylate functions, a suitable class of substrates of several synthetic and pharmacological studies, are easily available through Knoevenagel condensation of ethyl tert-butyl malonate and different aromatic aldehydes. The results have increased the potentialities of CeCl3·7H2O-NaI system as a type of water-tolerant green Lewis acid promoter for carbon-carbon bond forming procedures. 相似文献
19.
Qibo Liu 《Journal of fluorine chemistry》2011,132(2):78-87
(Z)-HFCCFZnI was stereoselectively synthesized from activated zinc dust and (Z)-HFCCFI that was synthesized from chlorotrifluoroethene in a sequential manner. Compared to (E)-HFCCFZnI, (Z)-HFCCFZnI was more challenging to prepare in terms of sluggish metallation and formation of by-products, and underwent slower and incomplete Negishi coupling with aryl iodides. In a modification of Negishi coupling, (E)-α,β-difluorostyrenes were stereospecifically prepared in good to excellent yields under mild conditions from aryl iodides and (Z)-HFCCFZnI with the co-catalysis of Pd(PPh3)4/Cu(I)Br. Experimental investigation and mechanistic rationalization suggested that Cu(I)Br would be a scavenger of free ligands for the facilitation of Pd(PPh3)2 formation, and a supplier of ligand for the metathesis process. Alternatively, (Z)-HFCCFSnBu3 and aryl iodides with an electron-withdrawing group underwent Stille-Liebiskind coupling to afford (E)-α,β-difluorostyrenes. 相似文献
20.
Takahiro Ichige 《Tetrahedron letters》2006,47(28):4843-4848
Both (E)- and (Z)-3-hydroxy-2-methyl-1-alkenyl iodides were stereoselectively synthesized from iodomethylated epoxides by treatment with sodium hexamethyldisilazane in DMF and with LDA in THF (or lithium 2,2,6,6-tetramethylpiperidide in THF), respectively. 相似文献