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CDI-mediated monoacylation of symmetrical diamines and selective acylation of primary amines of unsymmetrical diamines

A highly efficient and green protocol for monoacylation of symmetrical diamines and chemoselective acylation of primary amines of unsymmetrical diamines has been developed.

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A new approach to 6-nitro-1H-[1,4]-diazepines

2,3-Disubstituted 2,3-dihydro-6-nitro-1H-[1,4]-diazepines are prepared with easy experimental manipulations from formylated nitroenamine, which behaves as the synthetic equivalent of nitromalonaldehyde usable in organic media.

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Related Products of 1806-29-7, Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. 1806-29-7, Name is 2,2-Biphenol, molecular formula is C12H10O2. In a Article£¬once mentioned of 1806-29-7

Regioselective halogenation of biphenyls for preparation of valuable polyhydroxylated biphenyls and diquinones

Electron-rich biphenyls were selectively oxyfunctionalised through a halogenation-methoxylation sequence. The obtained biphenyl methyl ethers were then oxidised to the corresponding quinones. This strategy transforms commercially available biphenyls into both natural and bioactive oxidised compounds.

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Further characterization of mitsunobu-type intermediates in the reaction of dialkyl azodicarboxylates with P(III) compounds

Structural characterization of compounds analogous to the proposed intermediates in the Mitsunobu esterification process is achieved by the combined use of NMR spectroscopy and X-ray diffractometric studies. The results show that compounds (t-BuNH)P(mu-N-t-Bu)2P[(N-t-Bu)(N-(CO 2R)-N(H)(CO2R))] [R = Et (11), i-Pr (12)], obtained by treating [(t-Bu-NH)P-mu-N-t-Bu]2 (10) with diethylazodicarboxylate (DEAD) or diisopropylazodicarboxylate (DIAD), respectively, have a structure with the NH proton residing between the two nitrogen atoms ((P)N(t-Bu) and (P)N-N(CO2Et)); this is the tautomeric form of the expected betaine (t-BuNH)P(mu-N-t-Bu)2P+[(NH-t-Bu)(N-(CO 2R)-N-(CO2R)]. Treatment of ClP(mu-N-t-Bu) 2P[(N-t-Bu){N-(CO2-i-Pr)-N(H)(CO2-i-Pr)] (6) with 2,6-dicholorophenol affords (2,6-Cl2-C6H 3-O)P-(mu-N-t-Bu)2P+[(NH-t-Bu){N[(CO 2i-Pr)(HNCO2i-Pr)]}](Cl-)(2,6-Cl 2-C6H3-OH) (14) that has a structure similar to that of (CF3CH2O)P(mu-N-t-Bu)2P +[(NH-t-Bu){N[(CO2i-Pr)(HNCO2i-Pr)]}](Cl -) (13), but with an additional hydrogen bonded phenol. Both of these have the protonated betaine structure analogous to that of Ph3P +N(CO2R)NH(CO2R)(R?CO2) – (2) proposed in the Mitsunobu esterification. Two other compounds, (ArO)P(mu-N-t-Bu)2P+(NH-t-Bu){N(CO2i-Pr) (HNCO2i-Pr)}(Cl-) [Ar = 2,6-Me2C 6H3O- (15) and 2-Me-6-t-Bu-C6H3-O- (16)], are also prepared by the same route. Although NMR tube reactions of 11 or 12 with tetrachlorocatechol, catechol, 2,2?-biphenol, and phenol revealed significant changes in the 31P NMR spectra, attempted isolation of these products was not successful. On the basis of 31P NMR spectra, the phosphonium salt structure (t-BuNH)P(mu-N-t-Bu)2P +[(HN-t-Bu){N-(CO2R)-N(H)(CO2R)]-(ArO -) is proposed for these. The weakly acidic propan-2-ol or water did not react with 11 or 12, Treatment of 12 with carboxylic acids/p-toluenesulfonic acid gave the products (t-BuNH)P(mu-N-t-Bu)2P+[(HN-t- Bu){N-(CO2-i-Pr)-N(H)(CO2-i-Pr)](ArCO2-) [Ar = Ph (18), 4-Cl-C6H4CH2 (19), 4-Br-C 6H4 (20), 4-NO2-C6H4 (21)] and (t-BuNH)P(mu-N-t-Bu)2P+|(HN-t-Bu){N-(CO 2-i-Pr)-N(H)(CO2-i-Pr)](4-CH3-C 6H4SO3-) (22) that have essentially the same structure as 2. Compound 18 has additional stabilization by hydrogen bonding, as revealed by X-ray structure determination. Finally it is shown that the in situ generated (t-BuNH)P(mu-N-t-Bu)2P+[(HN-t-Bu) {N-(CO2Et)-N(H)(CO2Et)](4-NO2-C 6H4CO2-) can also effect Mitsunobu esterification. A comparison of the Ph3P-DIAD system with the analogous synthetically useful Ph3P-dimethyl acetylenedicarboxylate (DMAD) system is made.

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Synthesis, characterization, and reactivity of palladium(II) salen and oxazoline complexes

Two methods for the syntheses of palladium(II) salen complexes are described. The first involves template synthesis of the ligand in which bis(salicylaldehydato)palladium(II), 2, is initially synthesized and reacted with the appropriate diamine bridge to yield the desired palladium salen. The template synthesis approach suffers, however, from low overall yields (17-30%). Alternatively, treatment of bis(acetonitrile)palladium(II) chloride with the appropriate salen ligand under inert atmosphere yields the palladium salen complex in high yields (80-85%). [2-(2?-Hydroxyphenyl)-2-oxazolinato]palladium(II), 7, was also synthesized. All the palladium complexes were fully characterized spectroscopically. A single-crystal X-ray structure of 7 has been solved. In contrast to previous reports, complex 2 was found to be stable over weeks and remained suitable for the template syntheses. The catalytic activity of complex 2 in cyclopropanation of alkenes with ethyl diazoacetate (EDA) was investigated. The catalyst is not functional group tolerant and works best for styrene; turnover numbers (TON’s) of 45 were achieved. The availability of an open coordination site seems to be a prerequisite for catalytic decomposition of EDA.

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.1806-29-7, Name is 2,2-Biphenol, molecular formula is C12H10O2. In a Article£¬once mentioned of 1806-29-7, Product Details of 1806-29-7

Design, synthesis and organocatalysis of 2,2?-biphenol-based prolinamide organocatalysts in the asymmetric direct aldol reaction in water

In this work, 2,2?-biphenol-based prolinamide water-compatible C 2- and C 1-symmetrical organocatalysts were synthesized with the use of enantiopure N-Cbz-(S)-proline as chiral source. Under the optimal reaction conditions, the C 1-symmetrical organocatalyst performed efficiently in the direct aldol reactions in water, thus delivering the desired aldol adducts in high yields (up to 100% yield) with excellent stereocontrol (up to 97:3 dr and 98% ee). The observed stereochemical outcome of the direct aldol reactions in water was interpreted by the proposed transition state. Georg Thieme Verlag Stuttgart New York.

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Improved resolution methods for (R,R)- and (S,S)-cyclohexane-1,2-diamine and (R)- and (S)-BINOL

Starting from inexpensive L-(+)-tartaric acid, it was possible to resolve and obtain pure both enantiomers of trans-cyclohexane-1,2-diamine 1 and thence both enantiomers of BINOL 2, two of the most powerful, chiral inducing backbones in asymmetric catalysis. The modified method is very economic, not only due to an almost doubling of the overall yields of enantiomerically pure compounds (86% 1, 83% 2) but also due to the easy recovery of resolving agent 1 [66% (R,R)-1, 79% (S,S)-1] in the BINOL resolution. An improvement in the yield of the preparation of racemic BINOL is also recorded.

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Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.HPLC of Formula: C6H14N2, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 1436-59-5, in my other articles.

A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 1436-59-5, Name is cis-Cyclohexane-1,2-diamine, molecular formula is C6H14N2. In a Article£¬once mentioned of 1436-59-5, HPLC of Formula: C6H14N2

Synthesis and Pharmacological Evaluation of Heterocyclic Carboxamides: Positive Allosteric Modulators of the M1 Muscarinic Acetylcholine Receptor with Weak Agonist Activity and Diverse Modulatory Profiles

Targeting allosteric sites at M1 muscarinic acetylcholine receptors is a promising strategy for the treatment of Alzheimer’s disease. Positive allosteric modulators not only may potentiate binding and/or signaling of the endogenous agonist acetylcholine (ACh) but also may possess direct agonist activity (thus referred to as PAM-agonists). Recent studies suggest that PAM-agonists with robust intrinsic efficacy are more likely to produce adverse effects in vivo. Herein we present the synthesis and pharmacological evaluation of a series of pyrrole-3-carboxamides with a diverse range of allosteric profiles. We proposed structural modifications at top, core, or pendant moieties of a prototypical molecule. Although generally there was a correlation between the degree of agonist activity and the modulatory potency of the PAMs, some derivatives displayed weak intrinsic efficacy yet maintained strong allosteric modulation. We also identified molecules with the ability to potentiate mainly the affinity or both affinity and efficacy of ACh.

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A highly diastereo-and enantioselective copper(I)-catalyzed henry reaction using a bis(sulfonamide)-diamine ligand

A series of bis(sulfonamide)-diamine (BSDA) ligands were synthesized from commercially available chiral alpha-amino alcohols and diamines. The chiral BSDA ligand 3a, coordinated with Cu(I), catalyzes the enantioselective Henry reaction with excellent enantioselectivity (up to 99%). Moreover, with the assistance of pyridine, a CuBr-3a system promotes the diastereoselective Henry reaction with various aldehyde substrates and gives the corresponding syn-selective adduct with up to a 99% yield and 32.3:1 syn/anti selectivity. The enantiomeric excess of the syn adduct was 97%.

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Dynamic Refolding of Ion-Pair Catalysts in Response to Different Anions

Four distinct folding patterns are identified in two foldamer-type urea-thiourea catalysts bearing a basic dimethylamino unit by a combination of X-ray crystallography, solution NMR studies, and computational studies (DFT). These patterns are characterized by different intramolecular hydrogen bonding schemes that arise largely from different thiourea conformers. The free base forms of the catalysts are characterized by folds where the intramolecular hydrogen bonds between the urea and the thiourea units remain intact. In contrast, the catalytically relevant salt forms of the catalyst, where the catalyst forms an ion pair with the substrate or substrate analogues, appear in two entirely different folding patterns. With larger anions that mimic the dialkyl malonate substrates, the catalysts maintain their native fold both in the solid state and in solution, but with smaller halide anions (fluoride, chloride, and bromide), the catalysts fold around the halide anion (anion receptor fold), and the intramolecular hydrogen bonds are disrupted. Titration of catalyst hexafluoroacetylacetonate salt with tetra-n-butylammonium chloride results in dynamic refolding of the catalyst from the native fold to the anion receptor fold.

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