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Helicene-based chiral auxiliaries and chirogenesis

Helicenes are unique helical chromophores possessing advanced and well-controlled spectral and chemical properties owing to their diverse functionalization and defined structures. Specific modification of these molecules by introducing aromatic rings of differing nature and and supramolecular chirogenic hosts. This review aims to highlight these distinct structural features of helicenes; the different synthetic and supramolecular approaches responsible for their efficient chirality control; and their employment in the chirogenic systems, which are still not fully explored. It further covers the limitation, scope, and future prospects of helicene chromophores in chiral chemistry.

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Highly selective acylation of polyamines and aminoglycosides by 5-acyl-5-phenyl-1,5-dihydro-4: H -pyrazol-4-ones

5-Acyl-5-phenyl-1,5-dihydro-4H-pyrazol-4-ones, accessible from arylpropargyl phenyldiazoacetates, are highly selective acyl transfer reagents for di- and polyamines, as well as aminoalcohols and aminothiols. As reagents with a carbon-based leaving group, they have been applied for benzoyl transfer with a broad selection of substrates containing aliphatic amino in combination with other competing nucleophilic functional groups. The substrate scope and levels of selectivity for direct benzoyl transfer exceed those of known benzoylating reagents. With exceptional selectivity for acylation between primary amines bound to primary and secondary carbons, these new reagents have been used in direct site-selective monobenzoylation of aminoglycoside antibiotics.

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The proportionality constant is the rate constant for the particular unimolecular reaction. the reaction rate is directly proportional to the concentration of the reactant. I hope my blog about 21436-03-3 is helpful to your research., Electric Literature of 21436-03-3

Electric Literature of 21436-03-3, Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. 21436-03-3, Name is (1S,2S)-Cyclohexane-1,2-diamine, molecular formula is C6H14N2. In a Article£¬once mentioned of 21436-03-3

Asymmetric Michael addition of arylthiols to alpha,beta-unsaturated carbonyl compounds catalyzed by bifunctional organocatalysts

Bifunctional chiral organocatalysts comprising thiourea and tertiary amine groups were synthesized. They act as efficient catalysts for asymmetric Michael addition of arylthiols to alpha,beta-unsaturated carbonyl compounds. Enantioselectivity up to 85% has been achieved. Asymmetric alpha-protonation reaction (up to 60% ee) can be obtained in the presence of the bifunctional catalyst.

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Application of 21436-03-3, Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. 21436-03-3, Name is (1S,2S)-Cyclohexane-1,2-diamine, molecular formula is C6H14N2. In a Article£¬once mentioned of 21436-03-3

Highly enantioselective Michael addition of aromatic ketones to nitroolefins promoted by chiral bifunctional primary amine-thiourea catalysts based on saccharides

(Chemical Equation Presented) A new class of thiourea catalysts have been developed which integrate saccharide and primary amine moieties into one small organic molecule. These simple catalysts are shown to be highly enantioselective for direct Michael addition of aromatic ketones to a range of nitroolefins (up to 98% ee).

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Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.name: (1S,2S)-Cyclohexane-1,2-diamine. In my other articles, you can also check out more blogs about 21436-03-3

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Synthesis of 1,4-diazines by ring expansion of 1,3-diazines

Fully saturated piperazin-3-one and quinoxalin-3-one derivatives were prepared by reactions of 2-anilino-2-ethoxy-3-oxothiobutanoic acid anilide with aliphatic 1,2-diamines. An unusual ring expansion of the intermediate 1,3-diazines leads to 1,4-diazines. Moreover, quinoxalin-3-one derivatives from chiral trans-1,2-diaminocyclohexane were obtained with diastereoselectivity >95%.

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Trans/cis isomerization of [RuCl2{H2CC(CH 2PPh2)2)}(diamine)] complexes: Synthesis, spectral, crystal structure and DFT calculations and catalytic activity in the hydrogenation of alpha,beta-unsaturated ketones

Three complexes of the general formula trans/cis-[Ru(II)(dppme) (NN)Cl2] {dppme is H2CC(CH2PPh 2)2 and NN is 1,2-diaminocyclohexane (trans/cis-(1)) and 1-methyl-1,2-diaminopropane (trans-(2)} were obtained by reacting trans-[RuCl2(dppme)2] with an excess amount of corresponding diamine in CH2Cl2 as a solvent. The complexes were characterized by an elemental analysis, IR, 1H, 13C and 31P{1H} NMR, FAB-MS and UV-visible. The trans-(1) (kinetic product) readily isomerizes to the cis-(1) (thermodynamic product) and this process was followed by using 31P{1H} NMR, cyclic voltammetry and UV-vis spectroscopy. The electrochemical studies on complex (1) reveal that the Ru(III)/Ru(II) couples are sensitive to the isomer (trans/cis) formed. The cis-(1) was confirmed by X-ray structure and 31P{ 1H} NMR. Transfer-hydrogenation reactions for reduction of trans-4-phenyl-3-butene-2-one were conducted using complexes trans/cis-(1) and trans-(2). The electronic spectra of cis/trans-(1) in dichloromethane were calculated with the use of time-dependent DFT methods.

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Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.COA 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 21436-03-3, in my other articles.

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Three chiral cyanide-bridged Cr?Cu complexes: Synthesis, crystal structures and magnetic properties

Two trans-dicyanidochromium(III)-containing building blocks and one chiral copper(II) compound have been employed to assemble cyanide-bridged heterometallic complexes, resulting in three chiral cyanide-bridged Cr(III)?Cu(II) complexes, {[Cu(L1)2Cr(L3)(CN)2]ClO4}2 ¡¤ CH3OH ¡¤ H2O (1a, L1 = (S,S)-1,2-diaminocyclohexane, H2L3 =1,2-bis(pyri-dine-2-carboxamido)benzene), {[Cu(L2)2Cr(L2)(CN)2]ClO4}2 ¡¤ CH3OH ¡¤ H2O (1b, L2 = (R,R)-1,2-diaminocyclohexane) {[Cu(L3)2Cr(L4)(CN)2][Cr(L4)(CN)2]} ¡¤ CH3OH ¡¤ 2H2O (2), (H2L4 = 1,2-bis(pyridine-2-carboxamido)-4-chloroben-zene). All the three complexes have been characterized by elemental analysis, IR spectroscopy and X-ray structure determination. Single-crystal X-ray diffraction analysis shows that the two enantiomeric complexes 1a, 1b and the complex 2 belong to cyanide-bridged cationic binuclear structure type with ClO4 ? or the anionic cyanide building block as balance anion for complexes 1a, 1b or 2, respectively. Investigation of the magnetic properties of the complexes 1a and 2 reveals the weak ferromagnetic coupling between the neighboring Cr(III) and Cu(II) ions through the bridging cyanide group.

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C-H…NiIII interaction-driven homochiral M and P helices of neutral (R,R)-and (S,S)-bis(pyrrol-2-ylmethyleneamino)cyclohexane Ni II complexes

Reaction of (R,R)- and (S,S)-bis(pyrrol-2-ylmethyleneamino)cyclohexane with NiII(OAc)2¡¤4H2O afforded enantiomeric nickel(II) Schiff-base complexes (R,R)-1 and (S,S)-1, respectively. Rare C-H…NiII interactions were found to be responsible for the facile formation of homochiral M and P helices of the neutral, chiral, mononuclear complexes in crystal lattices. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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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. 21436-03-3, Name is (1S,2S)-Cyclohexane-1,2-diamine, molecular formula is C6H14N2. In a Article£¬once mentioned of 21436-03-3, name: (1S,2S)-Cyclohexane-1,2-diamine

Recognition of enantiomers with chiral molecular tweezers derived from (+)-or (-)-usnic acid

The synthesis of four stereoisomers of a chiral molecular tweezer using trans-1,2-diaminocyclohexane as spacer and two molecules of usnic acid as pincers is reported. The behavior of these chiral tweezers as chiral complexing agents was evaluated in NMR with various chiral esters containing an electron-poor aromatic ring to allow non-covalent aromatic-aromatic interactions.

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New insights on the active species and mechanism of cytotoxicity of salan-Ti(IV) complexes: A stereochemical study

Following the discovery of cisplatin, much effort has been devoted to the exploration of transition metal complexes as cytotoxic agents. We have recently introduced the highly efficient C2-symmetrical salan-Ti(IV) family of complexes, demonstrating high cytotoxicity toward colon and ovarian cells and enhanced hydrolytic stability in mixed organic/water solutions. The effect of stereochemistry is hereby reported, by comparing the cytotoxic activity and hydrolysis of pure enantiomers and their racemic mixture for four complexes of this family with different aromatic substitutions: para-Me, para-Cl, ortho-Cl, and ortho-OMe. These complexes include the trans-diaminocyclohexyl bridge, which enables ligand-to-metal chiral induction to give solely the Delta isomer when starting from the R,R ligand and vice versa. Different activity is obtained for the different stereochemical forms (Delta, Lambda, and rac) in two of the four complexes, where for the other two either all forms are inactive or all are highly active. Additionally, where not all are of similar activity, the racemic mixture is the least active of the three. We therefore conclude that the salan ligand is essential for the fruitful biological interaction, which probably involves a chiral cellular target. The activity of the racemate differing from that expected from a simple mixture of enantiomers operating separately may be explained by the involvement of a polynuclear active species, where different metal centers might be of different configurations. This is particularly supported by the different polynuclear products of hydrolysis obtained from an optically pure complex and from the racemic one, as analyzed crystallographically. The former is an all-R,R chiral C1-symmetrical homodimer, while the latter is an achiral R,R-S,SCi-symmetrical heterodimer obtained through chiral recognition.

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