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61.
Synthesis of Chiral Exocyclic Amines by Asymmetric Hydrogenation of Aromatic Quinolin‐3‐amines 下载免费PDF全文
Xian‐Feng Cai Ran‐Ning Guo Mu‐Wang Chen Lei Shi Prof. Yong‐Gui Zhou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7245-7248
Asymmetric hydrogenation of aromatic quinolin‐3‐amines was successfully developed with up to 94 % enantiomeric excess (ee). Introduction of the phthaloyl moiety to the amino group is crucial to eliminate the inhibition effect caused by the substrate and product, to activate the aromatic ring, and to improve the diastereoselectivity. This new methodology provides direct and facile access to chiral exocyclic amines. Notably, this report is the first on the highly enantioselective hydrogenation of aromatic amines. 相似文献
62.
63.
Inherently Chiral Macrocyclic Oligothiophenes: Easily Accessible Electrosensitive Cavities with Outstanding Enantioselection Performances 下载免费PDF全文
Prof. Francesco Sannicolò Prof. Patrizia R. Mussini Prof. Tiziana Benincori Dr. Roberto Cirilli Prof. Sergio Abbate Serena Arnaboldi Simone Casolo Dr. Ettore Castiglioni Prof. Giovanna Longhi Dr. Rocco Martinazzo Dr. Monica Panigati Dr. Marco Pappini Dr. Elsa Quartapelle Procopio Dr. Simona Rizzo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(47):15298-15302
Linear conjugated oligothiophenes of variable length and different substitution pattern are ubiquitous in technologically advanced optoelectronic devices, though limitations in application derive from insolubility, scarce processability and chain‐end effects. This study describes an easy access to chiral cyclic oligothiophenes constituted by 12 and 18 fully conjugated thiophene units. Chemical oxidation of an “inherently chiral” sexithiophene monomer, synthesized in two steps from commercially available materials, induces the formation of an elliptical dimer and a triangular trimer endowed with electrosensitive cavities of different tunable sizes. Combination of chirality with electroactivity makes these molecules unique in the current oligothiophenes literature. These macrocycles, which are stable and soluble in most organic solvents, show outstanding chiroptical properties, high circularly polarized luminescence effects and an exceptional enantiorecognition ability. 相似文献
64.
Dr. Hua Dong Dr. Jordi Ignés‐Mullol Dr. Josep Claret Dr. Lourdes Pérez Dr. Aurora Pinazo Prof. Dr. Francesc Sagués 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7396-7401
A chiral selection process in a self‐assembled soft monolayer of an achiral amphiphile as a consequence of its interaction with chiral species dissolved in the aqueous subphase, is reported. The extent of the chiral selection is statistically measured in terms of the enantiomorphic excess of self‐assembled submillimeter domains endowed with well‐defined orientational chirality that is unambiguously resolved using optical microscopy. Our results show that the emergence of chirality is mediated by electrostatic interactions and significantly enhanced by hydrophobic effects. This chiral chemical effect can be suppressed and even reversed by opposing a macroscopic physical influence, such as vortical stirring. This result gives evidence for the crucial role of hydrodynamic effects in supramolecular aggregation. 相似文献
65.
Exploring the Synthesis of a New Group of Chiral Ammonium Salts with Specific Configurations at the Stereogenic Nitrogen Centers 下载免费PDF全文
Dr. Prisca K. Eckert Christopher Golz Dr. Patrick Degen Cornelia Werner Prof. Dr. Heinz Rehage Prof. Dr. Carsten Strohmann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(12):3268-3272
A group of new chiral dications with a fixed, specific configuration at the stereogenic nitrogen center was created. Stereoselective synthesis and recrystallization give the diastereomerically and enantiomerically pure dications, including a chiral amphiphile with surface‐active properties. 相似文献
66.
Wei‐Li Li Dr. Ya‐Fan Zhao Dr. Han‐Shi Hu Prof. Dr. Jun Li Prof. Dr. Lai‐Sheng Wang 《Angewandte Chemie (International ed. in English)》2014,53(22):5540-5545
Chirality is vital in chemistry. Its importance in atomic clusters has been recognized since the discovery of the first chiral fullerene, the D2 symmetric C76. 1 A number of gold clusters have been found to be chiral, 2 raising the possibility to use them as asymmetric catalysts. The discovery of clusters with enantiomeric structures is essential to design new chiral materials with tailored chemical and physical properties. 3 Herein we report the first inherently chiral boron cluster of [B30]? in a joint photoelectron spectroscopy and theoretical study. The most stable structure of [B30]? is found to be quasiplanar with a hexagonal hole. Interestingly, a pair of enantiomers arising from different positions of the hexagonal hole are found to be degenerate in our global minimum searches and both should co‐exist experimentally because they have identical electronic structures and give rise to identical simulated photoelectron spectra. 相似文献
67.
Aram Hong Chang Min Choi Han Jun Eun Changseop Jeong Prof. Jiyoung Heo Prof. Nam Joon Kim 《Angewandte Chemie (International ed. in English)》2014,53(30):7805-7808
The CD spectroscopy of a chiral compound in solution yields an average CD value derived from all of the conformations of a chiral molecule. By contrast, CD spectroscopy of cold chiral molecules in the gas phase distinguishes specific conformers of a chiral molecule, but the weak CD effect has limited the practical application of this technique. Reported herein is the first resonant two‐photon ionization CD spectra of ephedrines in a supersonic jet using circularly polarized laser pulses, which were generated by synchronizing the oscillation of the photoelastic modulator with the laser firing. The spectra exhibited well‐resolved CD bands which were specific for the conformations and vibrational modes of each enantiomer. The CD signs and magnitudes of the jet‐cooled chiral molecules were very sensitive to their conformations and thus offered crucial information for determining the three‐dimensional structures of chiral species, as conducted in combination with quantum chemical calculations. 相似文献
68.
Enantioselective and Regioselective Pyrone Diels–Alder Reactions of Vinyl Sulfones: Total Synthesis of (+)‐Cavicularin 下载免费PDF全文
Peng Zhao Prof. Dr. Christopher M. Beaudry 《Angewandte Chemie (International ed. in English)》2014,53(39):10500-10503
The total synthesis of (+)‐cavicularin is described. The synthesis features an enantio‐ and regioselective pyrone Diels–Alder reaction of a vinyl sulfone to construct the cyclophane architecture of the natural product. The Diels–Alder substrate was prepared by a regioselective one‐pot three‐component Suzuki reaction of a non‐symmetric dibromoarene. 相似文献
69.
Qiongzheng Hu Prof. Shoujun Xu 《Angewandte Chemie (International ed. in English)》2014,53(51):14135-14138
Differential binding force has been used to precisely characterize the mechanical effect of a drug molecule binding to a DNA duplex. The high‐resolution binding forces measured by the force‐induced remnant magnetization spectroscopy (FIRMS) enable the binding behavior of drug molecules with different chirality and DNA of various sequences to be distinguished. The sequence specificity of Hg2+ and daunomycin was revealed by force spectroscopy for the first time, and the results are consistent with those obtained by other techniques. Furthermore, the two isomers of d,l ‐tetrahydropalmatine showed selectivity for two different DNA sequences. One particular useful feature of this approach is that the small molecules under study do not require any labels. 相似文献
70.
A theoretical study of the conformational profile of two diphosphines, PH2?PH2 and PH2?PHF, is carried using second‐order Møller–Plesset perturbation theory (MP2) computational methods. The chiral minima found are used to build homo‐ and heterochiral dimers. Six minima are found for the (PH2?PH2)2 dimers and 27 for the (PH2?PHF)2 dimers. Pnicogen and hydrogen bonds, the non‐covalent forces that stabilize the complexes, are characterized by Atoms in Molecules (AIM) and Natural Bond Orbital (NBO) methodologies. Those with several pnicogen bonds are more stable than those with hydrogen bonds. The chirodiastaltic energies amount to a total of 1.77 kJ mol?1 for the Ra:Ra versus Ra:Sa (PH2?PH2)2 dimers, 0.81 kJ mol?1 for the RSa:RSa versus RSa:SRa (PH2?PHF)2 dimers, and 2.93 kJ mol?1 for the RRa:RRa versus RRa:SSa (PH2?PHF)2 dimers. In the first and second cases, the heterochiral complex is favored whereas in the third case, the homochiral complex is favored. 相似文献