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41.
The ambido-, stereo- and enantioselectivity of the phosphoramide-promoted aldol reactions of α-oxy aldehyde trichlorosilyl enolates with benzaldehyde has been investigated. Analysis of the products from α-tert-butyldimethylsilyloxy α-deuterioacetaldehyde trichlorosilyl enolate confirmed that this 1,2-bis-silyloxyethene derivative reacted as a tert-butyldimethylsilyl enolate rather than trichlorosilyl enolate in the aldol reaction with very high ambidoselectivity. The phosphoramide-coordinated trichlorosilyl group acted as an organizing center for the aldol reaction. From the aldol process, excellent anti-diastereoselectivity could be achieved. The enantioselectivity remained moderate to low for both anti- and syn-diastereomer with a wide range of phosphoramide catalysts. α-Triisopropylsilyloxy, phenoxy and benzyloxy acetaldehyde trichlorosilyl enolates also reacted in a similar fashion with benzaldehyde to give aldol products with varying degrees of selectivities. 相似文献
42.
Claudia G. Avila-Ortiz 《Tetrahedron》2005,61(35):8372-8381
β2-(3,4-Dihydroxybenzyl)-β-alanine [β2-Homo-Dopa, 1] is a novel β-amino acid homologue of Dopa, the most successful therapeutic agent in the treatment of Parkinson's disease. Enantioenriched (R)-1 and (S)-1 were obtained via the diastereoselective alkylation of enantiopure pyrimidinone (R)- and (S)-3, chiral derivatives of β-alanine, with veratryl iodide. The major diastereomeric products (2S,5R)-4 and (2R,5S)-4 were hydrolyzed with 57% HBr, and the desired β-amino acids were purified by silica gel chromatography. Alternatively, enantioenriched (R)- and (S)-1 were prepared by means of the highly diastereoselective alkylation (3,4-dimethoxybenzyl iodide) of open-chain β-aminopropionic acid derivatives (R,R,S)-8 and (S,S,R)-8 containing the chiral auxiliary α-phenylethylamine. Finally, nearly enantiopure (R)- and (S)-1 were obtained by resolution of racemic N-benzyloxycarbonyl-2-(3,4-dibenzyloxybenzyl)-3-aminopropionic acid, rac-12, with (R)- or (S)-α-phenylethylamine, followed by catalytic hydrogenolysis. 相似文献
43.
Narayan G. Bhat Patricia Wawroski Gonzalo Perez-Garcia Mayra Elizondo 《Tetrahedron letters》2005,46(31):5153-5155
A convenient, novel diastereoselective synthesis of 1-trimethylsilyl-(E)-1,3-alkenynes and a convenient synthesis of alkyl trimethylsilylethynyl ketones based on Z-1-bromo-1-alkenylboronate esters are developed. α-Bromo-(Z)-1-alkenylboronate esters readily available using literature procedures smoothly undergo a reaction with trimethylsilylethynyllithium (derived from the deprotonation of trimethylsilylethyne with n-butyllithium) in tetrahydrofuran to provide the corresponding ‘ate’ complexes. These ‘ate’ complexes undergo intramolecular nucleophilic substitution reactions to afford the corresponding (E)-1-alkenylboronate esters containing trimethylsilylethynyl moiety which upon protonolysis with acetic acid provide the corresponding 1-trimethylsilyl-(E)-1,3-alkenynes in good yields (70-82%) and in high stereochemical purities (>98%). These intermediates upon oxidation with hydrogen peroxide and sodium acetate afford the corresponding alkyl trimethylsilylethynyl ketones in good yields (66-78%). 相似文献
44.
Cathodic reduction of phenacyl bromides N-acyl hydrazones lead to dimeric 1,4-diaryl-1,4-butanedione di-N-acylhydrazones, which give the corresponding 1-N-acylamino-2,5-diarylpyrroles in good yields. 相似文献
45.
应用分子力学和量子力学联合的ONIOM2(B3LYP/6-31G(d,p):UFF)计算方法研究了H-ZSM-5分子筛上乙烯二聚反应的机理. 用40T簇模型模拟ZSM-5分子筛位于孔道交叉点的酸性位,对乙烯二聚过程的分步反应和协同反应两种机理进行了考察. 对于分步反应机理,乙烯分子首先通过π-氢键作用在酸性位形成稳定的吸附络合物,再进一步发生质子化并生成乙醇盐中间体,随后乙醇盐与第二个乙烯分子发生碳-碳键结合形成丁醇盐产物. 第一步质子化和第二步碳链聚合的活化能分别为152.88和119.45 kJ/mol, 表明乙烯质子化反应为速控步骤. 对于协同反应机理,乙烯质子化、碳-碳键和碳-氧键生成同时进行,生成丁醇盐,反应的活化能为162.30 kJ/mol, 略高于分步反应机理中的速控步骤. 计算结果表明这两种反应机理之间存在相互竞争. 相似文献
46.
47.
A scalable synthesis of (−)-trans-2-(hydroxymethyl)-1,2,3,6-tetrahydropyridin-3-ol, a versatile chiral building block is described along with its transformation to (−)-trans-3-hydroxypipecolic acid. 相似文献
48.
Pengcheng Qian 《合成通讯》2013,43(21):3242-3250
An efficient Rh-catalyzed dimerization of diaryl acetylenes was achieved in the presence of Wilkinson catalyst, AgF2, and 1.5 equivalent of PhMgBr in toluene, providing the 1,2,3-triaryl naphthalene derivatives in moderate to good yields. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file. 相似文献
49.
Tiesheng Li Wenjian Xu Caiqin Tang Min Zhang Yangjie Wu Tokuji Miyashita 《Journal of Polymer Science.Polymer Physics》2012,50(2):139-147
A new series of copolymer poly(N‐hexadecylmeth acrylamide‐co‐bis(anthracen‐9‐ylmethyl) 2‐allylmalonate) [poly(HDMA‐co‐DAnMAMA)]s containing swallow‐tailed double anthracenyl groups and long alkyl group are designed and synthesized. The main route of the photochemical reaction of the p(HDMA‐DAnMAMA)copolymer Langmuir–Blodgett (LB) films is dimerization reaction between the anthracenyl groups under the irradiation of both 365 and 248 nm for limiting irradiation time, resulting to a fine negative‐tone pattern. On the other hand, the anthracenyl groups act just as photodecomposition group under 248 nm for longer irradiation time, resulting to a fine positive‐tone pattern. Consequently, positive‐tone and negative‐tone pattern are obtained by choosing not only a suitable irradiation light wavelength, but the irradiation time at 248 nm. Moreover, it is found that the exposed and unexposed regions of copolymer LB films irradiated at 248 nm have solubility differentiation in gold etchant (I2/NH4I/C2H5OH/H2O), that is to say, the gold photopatterns with the maximal resolution of the used mask can be obtained easily without any development process. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 50: 139–147, 2012 相似文献