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71.
Srivastava A Ghorai S Bhattacharjya A Bhattacharya S 《The Journal of organic chemistry》2005,70(17):6574-6582
A novel low-molecular mass tetrameric sugar derivative containing azobenzene core, 1, showed pronounced hydrogelation at micromolar concentration. Based on this observation, four related azobenzene based tetrameric sugar derivatives, 4-7, and three tetrameric sugar derivatives with a bis-terephthalamide core, 9-11, were also synthesized. However, none of these closely related analogues of the compound 1 showed effective gelation. The gel formed from 1 was characterized extensively using melting temperature analysis, UV-vis, FT-IR, circular dichroism spectroscopy, and scanning electron microscopy. The resultant gel exhibited impressive tolerance to the pH variation of the aqueous phase and gelated water in the pH range of 4-10. While UV-vis and CD spectroscopy indicated that pronounced aggregation of the azobenzene chromophores in 1 was responsible for gelation, FT-IR studies showed that hydrogen bonding is also a contributing factor in the gelation process. The melting of gel was found to depend on the pH of the aqueous medium in which gel was formed. The gel showed considerable photostability to UV irradiation, indicating tight intermolecular packing inside the gelated state that rendered azobenzene groups in the resultant aggregate refractory to photoisomerization. The electron micrographs of the aqueous gels of 1 showed the existence of spongy globular aggregates in such gelated materials. Addition of salts to the aqueous medium led to a delay in the gelation process and also caused remarkable morphological changes in the microstructure of the gel. 相似文献
72.
Organocatalytic,Enantioselective Synthesis of Cyclohexadienone Containing Hindered Spirocyclic Ethers through an Oxidative Dearomatization/Oxa‐Michael Addition Sequence
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Reddy Rajasekhar Reddy Dr. Satish Sonbarao Gudup Prof. Prasanta Ghorai 《Angewandte Chemie (International ed. in English)》2016,55(48):15115-15119
An unprecedented enantioselective oxa‐Michael reaction of α‐tertiary alcohols using cinchona‐alkaloid‐based chiral bifunctional squaramide catalysts is reported. An oxidative dearomatization of phenol followed by an enantioselective oxa‐Michael addition sequence provided a broad array of chiral sterically hindered tetrahydrofurans and tetrahydropyrans attached to a cyclohexadienone moiety in spiro fashion. In general, good yields and excellent enantioselectivities (up to 99 %) were observed. The chiral oxo‐cycles obtained have easily been transformed into chromans without disturbing the enantioselectivity. 相似文献
73.
Self-diffusivity, D, of diffusants in widely differing mediums such as liquids (e.g., solution), porous solids (e.g., guests in zeolites), or ions in polar solvents exhibit strong size dependence. We discuss the nature of the size dependence observed in these systems. Altogether, different theoretical approaches have been proposed to understand the nature of size dependence of D not only across these widely differing systems but even in just one medium or class of systems such as, for example, ions in polar solvents. But molecular dynamics investigations in the past decade have shown that the size dependence of self-diffusion in guest-porous solids could have origins in the mutual cancellation of forces that occurs when the size of the diffusant is comparable to the size of the void. The effect leading to the maximum in D is known as the levitation effect (LE). Such a cancellation is a consequence of symmetry. This effect exists in all porous solids irrespective of the geometrical and topological details of the pore network provided by the solid. Recent studies show that the levitation effect and size-dependent diffusivity maximum exists for uncharged solutes in solvents. One of the consequences of this is the breakdown in the Stokes-Einstein relationship over a certain range of solute-solvent size ratio. Experimental measurements of ionic conductivity over the past hundred years have found the existence of a size-dependent diffusivity maximum leading to violation of the Walden's rule for ions in polar solvents. Molecular dynamics simulations and experimental data suggest that even this maximum has its origin in LE. Simulation studies of impurity atom diffusion in close-packed solids as well as ions in superionic and other solids suggest the existence of a size-dependent diffusivity maximum in these materials as well. The levitation effect is a universal effect leading to a maximum in diffusivity of a diffusant in a variety of condensed matter phases. The only condition for its existence appears to be the presence of van der Waals or electrostatic interactions. 相似文献
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The first example of simple Re(2)O(7)-catalyzed direct dehydrative coupling between allylic alcohols with electron-deficient amines has been achieved under mild and open flask conditions. The protocol has also been successfully applied to benzylic and propargylic alcohols. The mechanistic proof for the S(N)1-type process has also been provided. 相似文献
78.
Hang J Ghorai P Finkenstaedt-Quinn SA Findik I Sliz E Kuwata KT Dussault PH 《The Journal of organic chemistry》2012,77(3):1233-1243
The first singlet excited state of molecular oxygen ((1)O(2)) is an important oxidant in chemistry, biology, and medicine. (1)O(2) is most often generated through photosensitized excitation of ground-state oxygen. (1)O(2) can also be generated chemically through the decomposition of hydrogen peroxide and other peroxides. However, most of these "dark oxygenations" require water-rich media associated with short (1)O(2) lifetimes, and there is a need for oxygenations able to be conducted in organic solvents. We now report that monoactivated derivatives of 1,1-dihydroperoxides undergo a previously unobserved fragmentation to generate high yields of singlet molecular oxygen ((1)O(2)). The fragmentations, which can be conducted in a variety of organic solvents, require a geminal relationship between a peroxyanion and a peroxide activated toward heterolytic cleavage. The reaction is general for a range of skeletal frameworks and activating groups and, via in situ activation, can be applied directly to 1,1-dihydroperoxides. Our investigation suggests the fragmentation involves rate-limiting formation of a peroxyanion that decomposes via a Grob-like process. 相似文献
79.
Arup Mukherjee Tamal K. Sen Dr. Pradip Kr. Ghorai Dr. Prinson P. Samuel Dr. Carola Schulzke Dr. Swadhin K. Mandal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(34):10530-10545
Herein, we report the synthesis and characterization of two organozinc complexes that contain symmetrical phenalenyl (PLY)‐based N,N‐ligands. The reactions of phenalenyl‐based ligands with ZnMe2 led to the formation of organozinc complexes [N(Me),N(Me)‐PLY]ZnMe ( 1 ) and [N(iPr),N(iPr)‐PLY]ZnMe ( 2 ) under the evolution of methane. Both complexes ( 1 and 2 ) were characterized by NMR spectroscopy and elemental analysis. The solid‐state structures of complexes 1 and 2 were determined by single‐crystal X‐ray crystallography. Complexes 1 and 2 were used as catalysts for the intramolecular hydroamination of unactivated primary and secondary aminoalkenes. A combined approach of NMR spectroscopy and DFT calculations was utilized to obtain better insight into the mechanistic features of the zinc‐catalyzed hydroamination reactions. The progress of the catalysis for primary and secondary aminoalkene substrates with catalyst 2 was investigated by detailed kinetic studies, including kinetic isotope effect measurements. These results suggested pseudo‐first‐order kinetics for both primary and secondary aminoalkene activation processes. Eyring and Arrhenius analyses for the cyclization of a model secondary aminoalkene substrate afforded ΔH≠=11.3 kcal mol?1, ΔS≠=?35.75 cal K?1 mol?1, and Ea=11.68 kcal mol?1. Complex 2 exhibited much‐higher catalytic activity than complex 1 under identical reaction conditions. The in situ NMR experiments supported the formation of a catalytically active zinc cation and the DFT calculations showed that more active catalyst 2 generated a more stable cation. The stability of the catalytically active zinc cation was further supported by an in situ recycling procedure, thereby confirming the retention of catalytic activity of compound 2 for successive catalytic cycles. The DFT calculations showed that the preferred pathway for the zinc‐catalyzed hydroamination reactions is alkene activation rather than the alternative amine‐activation pathway. A detailed investigation with DFT methods emphasized that the remarkably higher catalytic efficiency of catalyst 2 originated from its superior stability and the facile formation of its cation compared to that derived from catalyst 1 . 相似文献
80.
A Mukherjee TK Sen PK Ghorai PP Samuel C Schulzke SK Mandal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(34):10530-10545
Herein, we report the synthesis and characterization of two organozinc complexes that contain symmetrical phenalenyl (PLY)-based N,N-ligands. The reactions of phenalenyl-based ligands with ZnMe(2) led to the formation of organozinc complexes [N(Me),N(Me)-PLY]ZnMe (1) and [N(iPr),N(iPr)-PLY]ZnMe (2) under the evolution of methane. Both complexes (1 and 2) were characterized by NMR spectroscopy and elemental analysis. The solid-state structures of complexes 1 and 2 were determined by single-crystal X-ray crystallography. Complexes 1 and 2 were used as catalysts for the intramolecular hydroamination of unactivated primary and secondary aminoalkenes. A combined approach of NMR spectroscopy and DFT calculations was utilized to obtain better insight into the mechanistic features of the zinc-catalyzed hydroamination reactions. The progress of the catalysis for primary and secondary aminoalkene substrates with catalyst 2 was investigated by detailed kinetic studies, including kinetic isotope effect measurements. These results suggested pseudo-first-order kinetics for both primary and secondary aminoalkene activation processes. Eyring and Arrhenius analyses for the cyclization of a model secondary aminoalkene substrate afforded ΔH(≠) =11.3?kcal?mol(-1) , ΔS(≠) =-35.75?cal?K(-1) mol(-1) , and E(a) =11.68?kcal?mol(-1) . Complex 2 exhibited much-higher catalytic activity than complex 1 under identical reaction conditions. The in situ NMR experiments supported the formation of a catalytically active zinc cation and the DFT calculations showed that more active catalyst 2 generated a more stable cation. The stability of the catalytically active zinc cation was further supported by an in situ recycling procedure, thereby confirming the retention of catalytic activity of compound 2 for successive catalytic cycles. The DFT calculations showed that the preferred pathway for the zinc-catalyzed hydroamination reactions is alkene activation rather than the alternative amine-activation pathway. A detailed investigation with DFT methods emphasized that the remarkably higher catalytic efficiency of catalyst 2 originated from its superior stability and the facile formation of its cation compared to that derived from catalyst 1. 相似文献