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1.
Acetates derived from the adducts of the Baylis-Hillman reaction can be reacted in a regioselective manner with amines in the presence of palladium(0) catalyst to afford alpha-dehydro-beta-amino esters (2 and 3) in good yields. The regioselectivity of the reaction can be controlled by temperature and reaction medium leading to the synthesis of regioisomers 2 or 3. The alpha-dehydro-beta-amino acid 3 is a turn inducer, and the dipeptides 6 derived from it show the presence of an eight-membered intramolecular hydrogen bond. Also, cobalt(II) chloride catalyzes the cleavage of epoxy peptides with alpha-dehydro-beta-amino acid derivative 3b to afford the corresponding dipeptide derivatives 8, which exhibit an intramolecular hydrogen bond and thus mimic a beta-turn. This intramolecular hydrogen bonding preorganizes the corresponding diallylated peptide 8c for cyclization via ring-closing metathesis to afford the cyclic peptide 9 as a constrained mimic of a beta-turn. 相似文献
2.
Yutaka Morita Manfred Hesse Hans Schmid Avijit Banerji Julie Banerji Asima Chatterjee Willi E. Oberhnsli 《Helvetica chimica acta》1977,60(4):1419-1434
Alstonia scholaris: The structure of the indole alkaloid nareline Besides the known akuammidine, picralinal, picrinine and pseudoakuammigine a new indole alkaloid called nareline (M=352) was isolated from Alstonia scholaris R. BR. , which belongs to the plant family of Apocynaceae. Its structure 2 was deduced by single crystal X-ray diffraction. 2 represents the absolute configuration. The spectroscopic data of 2 and its derivatives (Scheme 1) as well as their chemical behavior support this structure. In biogenetic sense nareline is related to the bases akuammiline ( 4 ) and picraline ( 5 ) (Scheme 2). In contrast to those the C-atom 5 is exocyclic and represents an aldehyde group which forms together with the oxygen atom of the N (4)-hydroxylamine group a cyclic half acetale. - By oxidation (CrO3/CH3COOH) of 2 the oxindol derivative 19 (oxonareline) is formed which contains a cyclic acetal as a partial structure element (Scheme 4). 相似文献
3.
Extraction of promethium(III), uranium(VI), plutonium(IV), americium(III), zirconium(IV), ruthenium(III), iron(III) and palladium(II) has been carried out with a mixture of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and tributyl phosphate (TBP) in dodecane. The effects of nitric acid, TBP and CMPO concentrations on the extraction of these metal ions have been studied. The nature of the species of the above metal ions extracted into the organic phase has been suggested. 相似文献
4.
K.K. Banerji 《Tetrahedron》1973,29(10):1401-1403
The oxidation of mandelic acid and nine monosubstituted mandelic acids by acid permanganate, in the presence of fluoride ions, have been studied. The reaction is of first order with respect to each the oxidant, the substrate and hydrogen ions. The kinetic isotope effect, kH/kD = 3·76 at 25°. The oxidation exhibits a reaction constant ?+= ?2·23 ± 0·07 at 25°. The oxidation does not induce polymerisation of acrylonitrile and does not show any solvent isotope effect. The activation enthalpies entropies are linearly related (r = 0·979). A mechanism involving transfer of a hydride ion to the oxidant is proposed. 相似文献
5.
The oxidation of glycolic, lactic, malic, and a few substituted mandelic acids by 2,2′‐bipyridinium chlorochromate (BPCC) in dimethylsulphoxide leads to the formation of corresponding oxoacids. The reaction is first order each in BPCC and the hydroxy acids. The reaction is catalyzed by the hydrogen ions. The hydrogen ion dependence has the form: kobs = a + b [H+]. The oxidation of α‐deuteriomandelic acid exhibited a substantial primary kinetic isotope effect (kH/kd = 5.29 at 303 K). Oxidation of p‐methylmandelic acid was studied in 19 different organic solvents. The solvent effect has been analyzed by using Kamlet's and Swain's multiparametric equations. A mechanism involving a hydride ion transfer via a chromate ester is proposed. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 248–254, 2002 相似文献
6.
A novel low-valent titanium (LVT) mediated cleavage of N-allyl/benzyl amines is reported. Regio- and chemo-selective cleavages were also observed. 相似文献
7.
A new method for cyclodehydration of o-hydroxyaryl-β-ketols to 4-chromanones using HMPT is described. The method has general applicability. It is particularly useful for the cyclisation of labile intermediates as exemplified by the synthesis of cannabinoid synthon, 2-methyl-2-(4-methyl-3-pentenyl)-7-methoxy-4-chromanone. 相似文献
8.
The synthesis of chromenoflavone, cycloartocarpesin trimethyl ether (1b) has been achieved through the aroylation of lithium enolate of evodionol (2) with 2,4-dimethoxybenzoyl chloride followed by cyclodehydration of the β-diketone (3) with D-toluenesulphonic acid. 相似文献
9.
Kakali De Asoke Behera Indranil Banerjee Bharat Sarkar Santanu Ganguly Mridula Misra 《Journal of Radioanalytical and Nuclear Chemistry》2014,301(3):847-861
The aim of this study was to synthesis, a radiolabeled (99mTc) new somatostatin-analogue 6-hydrazinopyridine-3-carboxylic-acid (HYNIC)-Asn3-octreotate (99mTc-HYNIC-AATE), and to evaluate as a candidate for imaging somatostatin-receptor (SSTR)-positive tumors and also compare it with 99mTc-HYNIC-Tyr3-octreotide (99mTc-HYNIC-TOC). Synthesis was performed by Fmoc-solid-phase strategy and 99mTc labeled by SnCl2. Biodistribution and imaging properties of new radiopeptide were also studied in C6 tumor bearing rat. Radiolabeling was performed at high specific activities and it showed high binding-affinity for SSTR2. In biodistribution, radiopeptides have showed high and receptor-specific uptake in the SSTR2 positive organs, tumor with rapid renal excretion from non-target tissues. These results demonstrated that 99mTc-HYNIC-AATE is a new specific radioligand for scintigraphy of somatostatin-receptor-positive tumors. 相似文献
10.