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311.
The stereoselective synthesis of 2,4- and 2,5-disubstituted 1,3-oxazolidines is accomplished via Pd-catalyzed carboamination of O-vinyl-1,2-amino alcohol derivatives. The transformations generate cis-disubstituted products with good to excellent diastereoselectivity, and enantiomerically enriched substrates are converted without loss of optical purity. In addition to yielding synthetically useful products that are difficult to generate with existing methods, these transformations illustrate that electron-rich enol ethers are viable substrates for alkene carboamination processes. 相似文献
312.
A concise asymmetric synthesis of (+)-aphanorphine has been achieved via a new enantioconvergent strategy. A racemic γ-aminoalkene derivative is transformed into a 1:1 mixture of enantiomerically enriched diastereomers using an asymmetric Pd-catalyzed carboamination. This mixture is then converted to an enantiomerically enriched protected aphanorphine derivative by a Friedel-Crafts reaction, which generates a quaternary all-carbon stereocenter. The natural product is obtained in three additional steps. 相似文献
313.
The synthesis of tropane derivatives via intramolecular Pd-catalyzed alkene difunctionalization reactions is described. Enantiopure N-aryl-γ-aminoalkenes bearing an aryl or alkenyl halide adjacent to the amino group were converted to benzo- or cycloalkenyl-fused tropane products in good yield and with no loss of enantiopurity. 相似文献
314.
Babajan Banaganapalli Chaitanya Mulakayala Gowsia D Naveen Mulakayala Madhusudana Pulaganti Noor Ahmad Shaik Anuradha CM Raja Mohan Rao Jumana Yousuf Al-Aama Suresh Kumar Chitta 《Applied biochemistry and biotechnology》2013,171(7):1639-1657
Resveratrol (RVS) is a naturally occurring antioxidant, able to display an array of biological activities. In the present investigation, a new derivative of RVS, RVS(a), was synthesized, and its biological activity was determined on U937 cells. It was observed that RVS(a) showed pronounced activity on U937 cells than RVS. RVS(a) is able to induce apoptosis in tumor cell lines through subsequent DNA fragmentation. From the EMSA results, it was evident that RVS(a) was able to suppress the activity of NFkB by interfering its DNA binding ability. Furthermore, the molecular interaction analysis (docking and dynamics) stated that RVS(a) has strong association with the IkB-alpha site of NFkB compared with RVS; this binding nature of RVS(a) might be prevent the NFkB binding ability with DNA. The present findings represent the potential activity of propynyl RVS on U937 cells and signifying it as a one of putative chemotherapeutic drugs against cancer. 相似文献
315.
The use of the weak base Cs2CO3 in Pd-catalyzed carboamination reactions of N-protected gamma-aminoalkenes with aryl bromides leads to greatly increased tolerance of functional groups and alkene substitution. Substrates derived from (E)- or (Z)-hex-4-enylamines are stereospecifically converted to 2,1'-disubstituted pyrrolidine products that result from suprafacial addition of the nitrogen atom and the aryl group across the alkene. Transformations of 4-substituted pent-4-enylamine derivatives proceed in high yield to afford 2,2-disubstituted products, and cis-2,5- or trans-2,3-disubstituted pyrrolidines are generated in good yield with excellent diastereoselectivity from N-protected pent-4-enylamines bearing substituents at C1 or C3. The reactions tolerate a broad array of functional groups, including esters, nitro groups, and enolizable ketones. The scope and limitations of these transformations are described in detail, along with models that account for the observed product stereochemistry. In addition, deuterium labeling experiments, which indicate these reactions proceed via syn-aminopalladation of intermediate palladium(aryl)(amido)complexes regardless of degree of alkene substitution or reaction conditions, are also discussed. 相似文献
316.
Wolfe GM Crounse JD Parrish JD St Clair JM Beaver MR Paulot F Yoon TP Wennberg PO Keutsch FN 《Physical chemistry chemical physics : PCCP》2012,14(20):7276-7286
The C(5)-hydroperoxyenals (C(5)-HPALDs) are a newly-recognized class of multi-functional hydrocarbons produced during the hydroxyl radical (OH)-initiated oxidation of isoprene. Recent theoretical calculations suggest that fast photolysis of these compounds may be an important OH source in high-isoprene, low-NO regions. We report experimental constraints for key parameters of photolysis, OH reaction and ozone reaction of these compounds as derived from a closely-related, custom-synthesized C(6)-HPALD. The photolysis quantum yield is 1.0 ± 0.4 over the range 300-400 nm, assuming an absorption cross section equal to the average of those measured for several analogous enals. The yield of OH from photolysis was determined as 1.0 ± 0.8. The OH reaction rate constant is (5.1 ± 1.8) × 10(-11) cm(3) molecule(-1) s(-1) at 296 K. The ozone reaction rate constant is (1.2 ± 0.2) × 10(-18) cm(3) molecule(-1) s(-1) at 296 K. These results are consistent with previous first-principles estimates, though the nature and fate of secondary oxidation products remains uncertain. Incorporation of C(5)-HPALD chemistry with the above parameters in a 0-D box model, along with experimentally-constrained rates for C(5)-HPALD production from isomerization of first-generation isoprene hydroxyperoxy radicals, is found to enhance modeled OH concentrations by 5-16% relative to the traditional isoprene oxidation mechanism for the chemical regimes of recent observational studies in rural and remote regions. This enhancement in OH will increase if C(5)-HPALD photo-oxidation products also photolyze to yield additional OH or if the C(5)-HPALD production rate is faster than has been observed. 相似文献
317.
The intramolecular Pd-catalyzed carboetherification of alkenes affords 2-indan-1-yltetrahydrofuran products in moderate to good yield with good to excellent levels of diastereoselectivity. The stereochemical outcome of these reactions is dependent on the structure of the Pd catalyst. Use of PCy(3) or P[(4-MeO)C(6)H(4)](3) as the ligand for Pd leads to syn-addition of the arene and the oxygen atom across the double bond, whereas use of (+/-)-BINAP or DPP-benzene affords products that result from anti-addition. The catalyst-induced change in stereochemistry is likely due to a change in reaction mechanism. Evidence is presented that suggests the syn-addition products derive from an unprecedented transannular alkene insertion of an 11-membered Pd(Ar)(OR) complex. In contrast, the anti-addition products appear to arise from Wacker-type anti-oxypalladation. Studies on analogous Pd-catalyzed intramolecular carboamination reactions, which afford 2-indan-1-ylpyrrolidines that result from syn-addition, are also described. 相似文献
318.
The acoustic impedance spectrum was measured in the mouths of seven trumpeters while they played normal notes and while they practiced "bending" the pitch below or above the normal value. The peaks in vocal tract impedance usually had magnitudes rather smaller than those of the bore of the trumpet. Over the range measured, none of the trumpeters showed systematic tuning of the resonances of the vocal tract. However, all players commented that the presence of the impedance head in the mouth prevented them from playing the very highest notes of which they were normally capable. It is therefore possible that these players might use either resonance tuning or perhaps very high impedance magnitudes for some notes beyond the measured range. The observed lack of tuning contrasts with measurements for the saxophone which, like the trumpet, has weak resonances in the third and fourth octaves. Saxophonists are only able to play the highest range by tuning resonances of the vocal tract, so that the series impedance has a very strong peak at a frequency near that of the desired note. This difference is explained by the greater control that the trumpet player has over the natural frequency of the vibrating valve. 相似文献
319.
We present optitrode, a miniaturized flexible probe for integrated, localized light delivery and electrical recording. This device features an annular light guide with transparent polymer and fused silica layers surrounding a twisted-wire tetrode. We have developed a novel fabrication process, V-groove guided capillary assembly, to achieve high-precision, coaxial alignment of the various layers of the device. Optitrode with a length-to-diameter ratio ~500 (5 cm long, 100 μm diameter) has been fabricated, and both the electrical and optical functions have been characterized. The prototype can deliver 11% (110 mW) of the total laser power under abrupt bending angle ~25°. 相似文献