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21.
Microwave-induced organic reaction enhancement (‘MORE’) chemistry technique (open vessel; controlled microwave energy to stay below the boiling point of the reaction mixture) was used for the N-formylation of aliphatic and aromatic amines and amino heterocycles with aq formic acid (80%) on a multiple gram scale in a few minutes. 相似文献
22.
Wu A Mukhopadhyay P Chakraborty A Fettinger JC Isaacs L 《Journal of the American Chemical Society》2004,126(32):10035-10043
We report the synthesis and characterization of eight C-shaped methylene-bridged glycoluril dimers (1-8) bearing hydrogen-bonding amide groups on their aromatic rings. Compounds 1-6 undergo tight dimerization in CDCl3 solution (Ks > 9 x 10(5) M(-1)); binary mixtures of 1-7 form mixtures of homodimers and heterodimers in moderately selective dimerization processes (0.23 < or = Keq < or = 768; 0.253 < or = chiAB < 0.933). The high affinity formation of 1.1-6.6 is due to the commensurate nature of the geometrical constraints imposed by the pi-pi interactions and only two hydrogen bonds. The differential response of the strengths of the pi-pi interactions and H-bonds of 2.2 to changes in solvent polarity--from C6D6 to D2O--results in the formation of a solvent-independent isostructural aggregate that exhibits high affinity dimerization across the full range of solvents. 相似文献
23.
Guha S Goodson FS Corson LJ Saha S 《Journal of the American Chemical Society》2012,134(33):13679-13691
The recent emergence of anion-π interactions has added a new dimension to supramolecular chemistry of anions. Yet, after a decade since its inception, actual mechanisms of anion-π interactions remain highly debated. To elicit a complete and accurate understanding of how different anions interact with π-electron-deficient 1,4,5,8-naphthalenediimides (NDIs) under different conditions, we have extensively studied these interactions using powerful experimental techniques. Herein, we demonstrate that, depending on the electron-donating abilities (Lewis basicity) of anions and electron-accepting abilities (π-acidity) of NDIs, modes of anion-NDI interactions vary from extremely weak non-chromogenic anion-π interactions to chromogenic anion-induced charge-transfer (CT) and electron-transfer (ET) phenomena. In aprotic solvents, electron-donating abilities of anions generally follow their Lewis basicity order, whereas π-acidity of NDIs can be fine-tuned by installing different electron-rich and electron-deficient substituents. While strongly Lewis basic anions (OH(-) and F(-)) undergo thermal ET with most NDIs, generating NDI(?-) radical anions and NDI(2-) dianions in aprotic solvents, weaker Lewis bases (AcO(-), H(2)PO(4)(-), Cl(-), etc.) often require the photoexcitation of moderately π-acidic NDIs to generate the corresponding NDI(?-) radical anions via photoinduced ET (PET). Poorly Lewis basic I(-) does not participate in thermal ET or PET with most NDIs (except with strongly π-acidic core-substituted dicyano-NDI) but forms anion/NDI CT or anion-π complexes. We have looked for experimental evidence that could indicate alternative mechanisms, such as a Meisenheimer complex or CH···anion hydrogen-bond formation, but none was found to support these possibilities. 相似文献
24.
Dr. Pritam Ghosh Dr. Natalia Fridman Prof. Dr. Galia Maayan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(2):634-640
The construction of synthetic protein mimics is a central goal in chemistry. A known approach for achieving this goal is the self-assembly of synthetic biomimetic sequences into supramolecular structures. Obtaining different 3D structures via a simple sequence modification, however, is still challenging. Herein we present the design and synthesis of biomimetic architectures, via the self-assembly of distinct copper-peptoid duplexes. We demonstrate that changing only one non-coordinating side-chain within the peptoids—sequence-specific N-substituted glycine oligomers—leads to different supramolecular structures. Four peptoid trimers incorporating 2,2’-bipyridine and pyridine ligands, and a non-coordinating but rather a structure-directed bulky group were synthesized, and their solutions were treated with Cu2+ in a 1:1 ratio. Single-crystal X-ray analysis of the products revealed the self-assembly of each peptoid into a metallopeptoid duplex, followed by the self-assembly of multiple duplexes and their packing into a three-dimensional supramolecular architecture via hydrogen bonding and π–π interactions. Tuning the non-coordinating side-chain enables to regulate both the final structure being either a tightly packed helical rod or a nano-channel, and the pore width of the nano-channels. Importantly, all the metallopeptoids structures are stable in aqueous solution as verified by cryo-TEM measurements and supported by UV/Vis and EPR spectroscopies and by ESI-MS analysis. Thus, we could also demonstrate the selective recognition abilities of the nano-channels towards glycerol. 相似文献
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We describe here the propagation of light through a plano-convex spherical lens using the Stratton-Chu vector diffraction integrals. The values of the electric and magnetic fields on the two lens surfaces and at a point outside the lens are calculated by repeated use of the diffraction integrals and the intensity distribution in the focal region of the lens is determined. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
29.
[Reaction: see text]. A highly efficient synthetic method of carotenoid compounds has been developed on the basis of the sulfone coupling and double-elimination strategy. This method highlighted the sulfone-mediated coupling with the novel C(10) dialdehyde, 2,7-dimethyl-4-octenedial, which was easily prepared and efficiently utilized in the synthesis of the conjugated polyene chains. 相似文献
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