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Designing novel catalytic system for efficient synthesis of enantiomerically pure beta-hydroxy nitroalkanes is a challenging area of research. Herein, we have designed a chiral heterogeneous catalyst through the successful loading of chiral Cr(III)-salen complex over sulfonic acid functionalized SBA-15 material. The catalyst has been thoroughly characterized by powder XRD, N2 adsorption/desorption, XPS, HR-TEM, CHN, AAS analyses and FT-IR spectroscopy. The reactivity of the catalyst has been examined in the enantioselective Henry reaction, where different substituted aromatic, heteroaromatic as well as aliphatic aldehydes produced corresponding beta-hydroxy nitroalkanes with excellent product yields (up to 90%) and enantioselectivities (up to 91%). Moreover, this protocol has also been employed as the key-step to prepare enantiomerically pure drug (R)-(-)-isoproterenol from 3,4-dimethoxybenzaldehyde.

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Chiral Catalysts,
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Novel trans-4-hydroxy-L-proline-derived N,N?-dioxides have been developed and used as efficient organocatalysts for the one-pot three-component Strecker reaction with an aldehyde, (1,1-diphenyl)methylamine, and TMSCN. Both aromatic and aliphatic aldehydes were found to be suitable substrates. The corresponding alpha-amino nitriles were obtained in high yields with up to 95% ee (ee = enantiomeric excess) under mild conditions. Optically pure products could be obtained after a single recrystallization. The catalyst can be easily prepared from trans-4-hydroxy-L-proline and a diamine in three steps. Based on the experimental results and the observed absolute configurations of the products, a possible transition state has been proposed to explain the origin of the asymmetric induction.

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Chiral Catalysts,
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The exciton coupling between two cyanine dyes, characterized by intense and sharp absorption bands in the visible region, has been studied by UV-vis and CD spectroscopy because it provides a unique system of theoretical and applicational interests. Biscyanine dye 4b prepared from (1S,2S)-(+)-trans-1,2-cyclohexanediamine (1) shows two well-separated and strong electronic absorption bands at lambdamax 550 (epsilon 182 000) and 480 nm (epsilon 191 000). These visible bands are accompanied by strong exciton split CD Cotton effects, lambdaext 546 (Deltaepsilon -232) and 475 nm (Deltaepsilon +231); however, the signs of the split Cotton effects are opposite those of the bis p-methoxycinnamide) 2 which exhibits positive first and negative second Cotton effects. The stable conformation UV-VIS and CD spectra of the model biscyanine (1S,2S)-5 as calculated by molecular mechanics and the pi-electron SCF-CI-DV MO method yielded typical exciton-split CD curves with nearly equal negative and positive band areas (“regional sum rule”): visible, lambdamax 550 (epsilon 157 900) and 474 nm (epsilon 255 200); CD, lambdaext 550 (Deltaepsilon -140) and 474 nm (Deltaepsilon +136). The calculation indicated that the sign reversal in the bisignate CD of 4b in comparison with that of the bis(p-methoxycinnamide) 2 was due to a unique conformation of the two cyanine dye side chains; furthermore, it indicated that the large separation of the two bands in the visible and CD spectra was a result of strong exciton coupling between two cyanine dye electronic transitions characterized by their narrow bandwidths and location at long wavelength region. This is the first example in which exciton-split electronic absorption and CD bands appear as widely separated distinct peaks as large as 70 nm in solution.

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Chiral Catalysts,
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Chiral macrocyclic CrIII salen complexes have been synthesized, characterized, and used as catalysts in the asymmetric aminolysis of aromatic ester epoxides with various anilines to prepare the beta-amino-alpha-hydroxyl esters in very good yield (up to 95 %) along with high diastereo- and enantioselectivity (dr>99/1, ee up to 96 %) under the optimized condition particularly with CrIII complex 4, which was effectively recycled four times.

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Chiral Catalysts,
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A new flexible 2-ethylthiophene pendant-armed dialdehyde (H2tdd) was reacted with 1,3-propanediamine, [(S,S),(R,R),(±)]-1,2-diaminocyclohexane, and 1,2-bis(2-aminoethoxy)ethane, giving birth to 36-membered [2 + 2] Schiff-base macrocyclic trinuclear ZnII complex 1, 18-membered [1 + 1] mononuclear ZnII macrocycles 2-4, chiral/racemic 34-membered [2 + 2] dinuclear ZnII complexes 5-9, and 46-membered [2 + 2] dinuclear ZnII macrocycles 10-12 via ZnII ion template-assisted Schiff-base condensation. It is worth mentioning that the secondary template effects for nitrate and halide counterions have been observed in the 1,3-propanediamine involved imine condensation. In all [2 + 2] ZnII macrocycles, dinuclear complexes 5-9 display a full-folded molecular conformation, while trinuclear complex 1 and dinuclear complexes 10-12 exhibit distinct half-folded structures in the presence or absence of intramolecular I?-pistacking interactions between two phenolic rings of the dialdehyde component. Interestingly, a solvent-induced single-crystal-to-single-crystal transformation was first achieved for two types of solvated mononuclear macrocycles 3a and 3b (H2O vs CH3CN) with folded and unfolded ligand conformations. In addition, the photoluminescent properties were studied for this family of Schiff-base macrocyclic ZnII complexes as well as the dialdehyde precursor H2tdd.

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Enantiomers of a series of tripeptide derivatives with three stereogenic centers (±)-G1-G9 have been prepared from d- and l-alpha-amino acids as guests for chiral recognition by 1H NMR spectroscopy. In the meantime, a family of tetraaza macrocyclic chiral solvating agents (TAMCSAs) 1a-1d has been synthesized from d-phenylalanine and (1S,2S)-(+)-1,2-diaminocyclohexane. Discrimination of enantiomers of (±)-G1-G9 was carried out in the presence of TAMCSAs 1a-1d by 1H NMR spectroscopy. The results indicate that enantiomers of (±)-G1-G9 can be effectively discriminated in the presence of TAMCSAs 1a-1d by 1H NMR signals of multiple protons exhibiting nonequivalent chemical shifts (DeltaDeltadelta) up to 0.616 ppm. Furthermore, enantiomers of (±)-G1-G9 were easily assigned by comparing 1H NMR signals of the split corresponding protons with those attributed to a single enantiomer. Different optical purities (ee up to 90%) of G1 were clearly observed and calculated in the presence of TAMCSAs 1a-1d, respectively. Intermolecular hydrogen bonding interactions were demonstrated through theoretical calculations of enantiomers of (±)-G1 with TAMCSA 1a by means of the hybrid functional theory with the standard basis sets of 3-21G of the Gaussian 03 program.

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Chiral Catalysts,
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A simple and facile route has been described for the synthesis of macrocyclic tetraamides. This method is applicable for the preparation of a variety of macrocyclic tetraamides of various heteroatom substitutions.

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A generalized protocol for the synthesis of chiral (NH)2P2 macrocycles allows changing the linker between the phosphines and gives access to a family of such ligands, as demonstrated for the propane-1,3-diyl analogue. The corresponding complexes based on earth-abundant and nontoxic iron were applied as catalysts in the asymmetric transfer hydrogenation of polar double bonds. Thanks to the ligand modularity and to the use of tunable isonitriles as ancillary ligands, the catalyst system can be individually optimized for each substrate to give high enantioselectivity (up to 99.9% conversion and 99.6% ee, TOF up to >3950 h-1) for a broad scope of 26 substrates.

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Chiral Catalysts,
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Chiral P,N-ligands with pseudo-C2 and pseudo-Cs symmetry based on chiral pyrrolidine and phospholane rings or on dinaphthatodihydroazepino and dinaphthatodihydrophosphepino moieties were prepared and assessed in the palladium-catalyzed allylic substitutions of allylic acetates. Higher selectivity was achieved with pseudo-C2-symmetric ligands based on the binaphthyl skeleton than with the analogous C2-symmetric P,P- and N,N-analogues. Pseudo-C2-type ligands had properties superior to those of pseudo-meso-type ligands when 1,3-diphenyl-2-propenyl acetate was used as a substrate, whereas the reverse situation was found for 3-cyclohexenyl acetate. Chirally flexible ligands, prepared by substitution of one of the rigid binaphthyl skeletons for a flexible biphenyl system, were found to induce chirality to the same extent as a 1:1 mixture of the rigid ligands.

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Styrene copolymers containing 5?50 mol % of a comonomer with a salen catalytic-active moiety are synthesized by using ATRP in solution. Control of the synthesis is obtained only when the salen comonomer incorporation is less than 10 mol %. In those conditions, first-order kinetics, linear increase of Mn versus time and monomodal narrow molar mass distributions with molar mass dispersities Dh in the range 1.28?1.33 are satisfactorily achieved. For copolymers with higher incorporated salen comonomer, control of the reaction progressively disappears with dispersities increasing with salen comonomer incorporation up to Dh = 1.72. Cobalt complexation of those copolymers allows high yield and selectivity in the catalysis of the dynamic hydrolytic kinetic resolution of epibromohydrin. In spite of the loss of polymerization control, the highest (50%) salen incorporation yields the best catalytic results. Under these conditions, the high concentration of Co catalytic sites might favor the formation of bimetallic complexes responsible for the high activity and enantioselectivity.

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Chiral Catalysts,
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