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101.
Starting from trifluoromethyl β-dicarbonyl compounds, a rare loss of CF3CO was observed in the amination reactions performed under heterogeneous conditions using NsONHCO2Et as the aminating agent and CaO or NaH as the base, while corresponding nonfluorinated β-dicarbonyl compounds under analogous conditions give non deacylated aminated compounds. This reaction can facilitate a direct synthesis of N-substituted α-amino esters or α-amino ketones. 相似文献
102.
The thermal decarboxylation of three dicarboxylic perfluoropolyether potassium salts of relatively short chain length has been investigated and the products and kinetics of the main reactions have been defined. From the rate constants and Arrhenius parameters data, the second decarboxylation appears to be quantitatively rather close to the first. 相似文献
103.
Vanessa Gouge 《Tetrahedron letters》2004,45(4):773-776
2,2-Difluoro-3-(2-hydroxy-1 R-phenylethylamino)-3 S-phenylpropionic acid 3, obtained by a Reformatsky-type reaction of ethyl bromodifluoroacetate with (4R)-2,4-diphenyloxazolidine, was used as a classical carboxylic acid in the Ugi reaction to prepare various difluorinated pseudopeptides 5a-n. Compounds 5 were then deprotected by hydrogenolysis to furnish difluorinated pseudopeptides 6. 相似文献
104.
105.
Previous studies have established that the extended coordination model of solvation can satisfactorily account for the variation in the transfer enthalpies of solutes in mixed-solvent systems. The model parameter relating to the solute-induced disruption of the solvent structure shows a marked dependence on the nature of the mixed solvent. In the present paper we report the transfer enthalpies of acetonitrile from water to aqueous methanol, ethanol and dimethylsulphoxide (DMSO) systems. Analysis of these in terms of the extended coordination model confirms both the model's ability to account for the experimental data, and the variability of the structural disruption parameter. The solvation parameters recovered from the analyses indicate that the net effect of acetonitrile on the solvent structure is a breaking of solvent-solvent bonds. The extent of bond breaking of the solvent increases from MeOH to EtOH. 相似文献
106.
107.
Gerd-Volker Röschenthaler Michael Yu. Belik Alexander E. Sorochinsky 《Tetrahedron》2006,62(42):9902-9910
Addition of diethyl lithiodifluoromethylphosphonate to enantiomerically pure aromatic, heteroaromatic, and aliphatic aldehyde-derived sulfinimines afforded N-sulfinyl α,α-difluoro-β-aminophosphonates with generally good enantioselectivity and in high yield. The reaction with acetophenone-derived sulfinimine resulted in the formation of the addition product with high diastereoselectivity and in only moderate yield. A two-step deprotection involving treatment of diastereomerically pure N-sulfinyl α,α-difluoro-β-aminophosphonates with trifluoroacetic acid in EtOH followed by refluxing with 10 N HCl provided enantiopure α,α-difluoro-β-aminophosphonates and α,α-difluoro-β-aminophosphonic acids. The N-Cbz derivative of (R)-2-amino-1,1-difluoro-2-phenylethylphosphonate was a convenient starting point for the preparation of corresponding difluorophosphonate monoester, difluorophosphonic acid, and difluorophosphonamidic acid. At 21 °C difluorophosphonamidic acid was stable in aqueous solution at pH above 5. 相似文献
108.
Antonella Leggio 《Tetrahedron》2007,63(34):8164-8173
A highly efficient and practical synthesis of peptides in solution phase has been developed. The procedure is based on the use of p-nitrobenzenesulfonyl (nosyl) group for the protection of the amino function of α-amino acids. Every step of the procedure, protection of the amino function by the nosyl group, formation of the peptide bond, and removal of the sulfonamide group, is characterized by high yields and excellent purity of the final products. The described strategy allows the preparation of short peptide sequences keeping the chiral integrity of amino acid precursors. Compatibility of nosyl group with the side-chain protecting groups used in Fmoc-based strategy is demonstrated. The method here presented is an alternative strategy that could provide advantages for future peptide synthesis. 相似文献
109.
用ab initio方法, 在MP2/6-31G**水平下讨论了α-乙酰氧基-亚硝基吡咯烷(α-Acetoxy-NPYR)在各种条件下的解离反应机理, 并对形成终致癌物B, C, D的代谢机理进行研究. 发现在OH-和H2O作用下的解离都遵循羟基进攻羰基机理, OH-作用下是一个经四面体中间体阴离子的无位垒过程, H2O作用下有相对高的活化能(165.36 kJ/mol). H3O+作用下是先形成阳离子产物的SN1过程, 并没有发现遵循两种综合的解离情形. 同时, 羟基化产物异构化为终致癌物B, C, D是一个相对容易进行的过程. 相似文献
110.