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131.
132.
David E Perrin J Pellet-Rostaing S Fournier dit Chabert J Lemaire M 《The Journal of organic chemistry》2005,70(9):3569-3573
[reaction: see text] Benzo[b]thiophene derivatives are important in part because of their use as selective estrogen receptor modulators. They are usually synthesized by intramolecular cyclization. Here, we propose a method for the synthesis of 2-arylbenzo[b]thiophenes with heteroatoms at the 3-positions directly from the benzo[b]thiophene core by using an aromatic nucleophilic substitution reaction and Heck-type coupling. This methodology provides 2-aryl-3-amino or phenoxybenzo[b]thiophenes in about 35% overall yield in 5 steps. 相似文献
133.
A symmetric ditopic molecular receptor (3), containing two identical hydrogen-bonding recognition subunits, was designed and synthesized. These subunits are capable of binding substrates with complementary donor and acceptor sites to form a supramolecular complex through hydrogen bonding. Receptor 3 was designed to accept two guest molecules, which are held in close proximity within the supramolecular species. The substrate molecule, 4-methyl-7-O-hexylcoumarin (1 c), forms a 2:1 complex with a binding constant of 150 m(-1) for the second substrate, passing first through a 1:1 complex with an affinity constant of 510 m(-1). The orientation of two molecules of 1 c when bound to the template leads to the selective formation of the trans-syn [2+2] photoproduct 2 cB upon irradiation. Other photoproducts typically produced in the absence of the template are suppressed. 相似文献
134.
In this work we have examined the nitration by acetyl nitrate of a range of activated and deactivated aromatic substrates in two ionic liquids and compared the results to the same reaction in dichloromethane. Both ionic liquids are stable to the reaction conditions, and in both ionic liquids the yields of reaction are higher after unit time than the same reactions in dichloromethane, although the regioselectivity is little affected by solvent choice. This result gives further support to the suggestion that in the ionic liquid, acetyl nitrate dissociates to give the nitronium ion, and that this is the effective nitrating agent here. However, it is shown that [bmpy][N(Tf)(2)] is a better solvent for aromatic nitration than [bmpy][OTf]. This is due to the ease of formation of nitronium ion in the former ionic liquid, and is consistent with the fact that [bmpy][N(Tf)(2)] is a weaker hydrogen bond acceptor solvent than [bmpy][OTf]. Finally, a method by which [bmpy][N(Tf)(2)] may be recovered and reused for aromatic nitration has been demonstrated. 相似文献
135.
Barluenga S Moulin E Lopez P Winssinger N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(17):4935-4952
A modular synthesis for pochonin C and radicicol is reported. The two natural products were prepared in seven and eight steps, respectively, from three readily available fragments. Alternative syntheses of these compounds were achieved using a combination of polymer-bound reagents and solid phase reactions. The conformation of the two natural products was studied and compared by using 2D NMR spectroscopy. 相似文献
136.
Dr. Emilie R. Mainz Prof. Qunzhao Wang Prof. David S. Lawrence Prof. Nancy L. Allbritton 《Angewandte Chemie (International ed. in English)》2016,55(42):13095-13098
Tools to evaluate oncogenic kinase activity in small clinical samples have the power to guide precision medicine in oncology. Existing platforms have demonstrated impressive insights into the activity of protein kinases, but these technologies are unsuitable for the study of kinase behavior in large numbers of primary human cells. To address these limitations, we developed an integrated analysis system that utilizes a light‐programmable, cell‐permeable reporter deliverable simultaneously to many cells. The reporter's ability to act as a substrate for Akt, a key oncogenic kinase, was masked by a 2‐4,5‐dimethoxy 2‐nitrobenzyl (DMNB) moiety. Upon exposure to ultraviolet light and release of the masking moiety, the substrate sequence enabled programmable reaction times within the cell cytoplasm. When coupled to automated single‐cell capillary electrophoresis, statistically significant numbers of primary human cells were readily evaluated for Akt activity. 相似文献
137.
138.
Dr. Emilie Moulin Dr. Gad Fuks Prof. Dr. Mounir Maaloum Prof. Dr. Eric Buhler Prof. Dr. Nicolas Giuseppone 《Angewandte Chemie (International ed. in English)》2016,55(2):703-707
An acid–base switchable [c2]daisy chain rotaxane terminated with two 2,6‐diacetylamino pyridine units has been self‐assembled with a bis(uracil) linker. The complementary hydrogen‐bond recognition patterns, together with lateral van der Waals aggregations, result in the hierarchical formation of unidimensional supramolecular polymers associated in bundles of muscle‐like fibers. Microscopic and scattering techniques reveal that the mesoscopic structure of these bundles depends on the extended or contracted states that the rotaxanes show within individual polymer chains. The observed local dynamics span over several length scales because of a combination of supramolecular and mechanical bonds. This work illustrates the possibility to modify the hierarchical mesoscopic structuring of large polymeric systems by the integrated actuation of individual molecular machines. 相似文献
139.
140.
Positive operators on certain polyhedral cones with the property that the group inverse of the operator is equal to some power of the operator are characterized. The special case of the Moore-Penrose inverse is also considered. 相似文献