排序方式: 共有81条查询结果,搜索用时 46 毫秒
1.
The interaction of Me3SiOTf and (C6F5)3SiOTf with enamines generating α-silyl-substituted iminium ions is investigated. A trimethylsilyl iminium cation is formed as a long-lived species observable by NMR spectroscopy, whilst the tris(pentafluorophenyl)silyl analogue is very labile and prone to the loss of a proton. On the basis of the latter phenomenon, a method for the synthesis of β-silyl enamines is proposed. 相似文献
2.
Mohammad Ali Bigdeli Abbas Rahmati Hossein Abbasi-Ghadim Gholam Hossein Mahdavinia 《Tetrahedron letters》2007,48(26):4575-4578
Aromatic amines have been synthesized efficiently from enamines using SnCl4 and SbCl5 in CH2Cl2 at room temperature. 相似文献
3.
《Tetrahedron letters》2004,45(30):5799-5801
(+)-β-Hydroxymethylenecamphor 1 and enamines 2a-e were transformed into chiral camphor-based pyridine derivatives 3a-e via a tandem condensation reaction in good yields. 相似文献
4.
Condensation of readily available 5-(aminoalkyl)furan-2-ones, derived from the Mannich-type reaction between 2-silyloxyfurans and acyliminium ions, with an α-unsubstituted aliphatic aldehyde leads to substituted 1,2,3,4-tetrahydropyridines in a process involving an enamine conjugate addition. Reduction of the tetrahydropyridine double bond then affords 3,4,5-tri- or 3,4,5,6-tetra-substituted piperidines stereoselectively. 相似文献
5.
Jinsong Zhang Chris Taylor Erich Bowman Leo Savage-Low Michael W. Lodewyk Larry Hanne Guang Wu 《Tetrahedron letters》2013
A process for synthesizing 1,4-benzodioxin, through oxidation of a phenol to an o-quinone followed by treatment with an enamine, has been developed. Adduct stereochemistry is found to be retained via this one-pot reaction. The method uses hypervalent iodine reagent under mild conditions and is compatible with a wide scope of phenols and enamines. 相似文献
6.
Uroš Grošelj Dieter Seebach D. Michael Badine W. Bernd Schweizer Albert K. Beck Ingo Krossing Petra Klose Yujiro Hayashi Tadafumi Uchimaru 《Helvetica chimica acta》2009,92(7):1225-1259
Structures of the reactive intermediates (enamines and iminium ions) of organocatalysis with diarylprolinol derivatives have been determined. To this end, diarylprolinol methyl and silyl ethers, 1 , and aldehydes, Ph? CH2? CHO, tBu? CH2? CHO, Ph? CH=CH? CHO, are condensed to the corresponding enamines, A and 3 (Scheme 2), and cinnamoylidene iminium salts, B and 4 (Scheme 3). These are isolated and fully characterized by melting/decomposition points, [α]D, elemental analysis, IR and NMR spectroscopy, and high‐resolution mass spectrometry (HR‐MS). Salts with BF4, PF6, SbF6, and the weakly coordinating Al[OC(CF3)3]4 anion were prepared. X‐Ray crystal structures of an enamine and of six iminium salts have been obtained and are described herein (Figs. 2 and 4–8, and Tables 2 and 7) and in a previous preliminary communication (Helv. Chim. Acta 2008 , 91, 1999). According to the NMR spectra (in CDCl3, (D6)DMSO, (D6)acetone, or CD3OD; Table 1), the major isomers 4 of the iminium salts have (E)‐configuration of the exocyclic N?C(1′) bond, but there are up to 11% of the (Z)‐isomer present in these solutions (Fig. 1). In all crystal structures, the iminium ions have (E)‐configuration, and the conformation around the exocyclic N‐C? C‐O bond is synclinal‐exo (cf. C and L ), with one of the phenyl groups over the pyrrolidine ring, and the RO group over the π‐system. One of the meta‐substituents (Me in 4b , CF3 in 4c and 4e ) on a 3,5‐disubstituted phenyl group is also located in the space above the π‐system. DFT Calculations at various levels of theory (Tables 3–6) confirm that the experimentally determined structures (cf. Fig. 10) are by far (up to 8.3 kcal/mol) the most stable ones. Implications of the results with respect to the mechanism of organocatalysis by diarylprolinol derivatives are discussed. 相似文献
7.
Annegret Tillack Harald Trauthwein Christian G. Hartung Martin Eichberger Stephan Pitter Achim Jansen Matthias Beller 《Monatshefte für Chemie / Chemical Monthly》2000,131(12):1327-1334
Summary. The oxidative amination of styrene with secondary amines in the presence of cationic rhodium catalysts yields regiospecifically
the corresponding anti-Markovnikov enamines. Styrene as the hydrogen acceptor gave concomitantly ethylbenzene. In the presence of 1,5-cyclooctadiene (cod) preferential reduction to cyclooctene takes place. The addition of cod reduces the rate of the reaction, but also the amount of ethylbenzene produced. Here, for the first time the ratio of enamine:
ethylbenzene is > 1, which is favourable in case of more expensive styrene derivatives. A screening of various ligands for
oxidative amination reveals that hemilabile 2-(ω-phosphino-n-alkyl)-pyridines are superior ligands for this reaction compared to simple alkyl and aryl phosphines.
Received May 30, 2000. Accepted July 11, 2000 相似文献
8.
Matthew J. Cook 《Tetrahedron letters》2005,46(2):297-300
The Petasis olefination of unsymmetrical oxalates and oxalate monoesters/monoamides (tert-BuO2CC(O)X, where X = OR, NR2) is highly regioselective and provides pyruvate-based enol ether and enamine derivatives. The olefination step occurs under conventional thermal conditions, but is dramatically improved--shorter reaction times and higher yields--when promoted by microwave irradiation. 相似文献
9.
Stephanie Knüppel 《Journal of organometallic chemistry》2005,690(1):14-32
Treatment of 6-methyl-6-dimethylaminofulvene (2a) with methyl lithium in ether results in a deprotonation reaction to yield the enamino-substituted lithium cyclopentadienide reagent 3a. Its reaction with zirconium tetrachloride (0.5 molar equivalents) results in the formation of the [1-dimethylaminobutadien-1,3-diyl-bis(cyclopentadienyl)]zirconium dichloride product 4a. The unsaturated ansa-metallocene is probably formed via a Lewis acid-catalyzed Mannich-type carbon-carbon coupling reaction of an in situ generated bis[(dimethylaminoethenyl)cyclopentadienyl]ZrCl2 intermediate. A number of related examples of this condensation reaction at the intact Group 4 bent metallocene framework is described, using different amino-substituents and Ti, Zr and Hf systems. Three examples of the unsaturated ansa-metallocene systems were characterized by X-ray diffraction. In a few cases it was possible to isolate the open (enamino-Cp)2ZrCl2 complexes. In the case of, e.g., (piperidinoethenylcyclopentadienyl)2ZrCl2 (13c) treatment with a catalytic quantity of the Lewis acid ZrCl4 or the Brønsted acid resulted in a clean conversion to the respective Mannich condensation product, here the ansa-metallocene complex 4c. The strongly electrophilic borane HB(C6F5)2 did not catalyze the CC-coupling reaction under the applied reaction conditions but added cleanly to the enamino-CC double bond of, e.g., 13c to yield a cyclic nitrogen donor-stabilized hydroboration product (19). 相似文献
10.
John K. Gallos Vassiliki C. Sarli Zoe S. Massen Anastassia C. Varvogli Constantina Z. Papadoyanni Sofia D. Papaspyrou Nicolaos G. Argyropoulos 《Tetrahedron》2005,61(3):565-574
A new method for the synthesis of racemic non-proteinogenic α-amino acids has been developed, which involves (i) hetero-Diels-Alder addition of ethyl 2-nitrosoacrylate to electron rich alkenes such as enol ethers, enamines and allylsilanes, (ii) NaCNBH3 reduction of the CN bond in the oxazines thus generated, the stereochemistry of the products being controlled by epimerisation of the thermodynamically less stable isomer to the more stable one, (iii) protection of the N-H group as N-Boc and (iv) finally, N-O bond cleavage of both free and protected products to give proline or bis-homoserine derivatives, respectively. An example with concomitant reduction of the carboxylate group, resulting in the formation of the respective amino alcohol is reported. Applying this methodology to a homochiral enol ether, the protected parent d-proline was prepared in enantiomerically pure form, whereas the asymmetric synthesis of the respective bis-homoserine was unsuccessful. 相似文献