01/9/2021 News Archives for Chemistry Experiments of 18531-94-7

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(Chemical Equation Presented) Rhodium-catalyzed hydroborations of trisubstituted alkenes are generally slow and often suffer from competing alkene isomerization. In contrast, the trisubstituted alkene moieties contained within the framework of a beta,gamma-unsaturated amide undergo facile reaction, perhaps facilitated by carbonyl directing effects and two-point binding of the substrate to the rhodium catalyst. Stereoisomeric substrates, for example, (E)- and (Z)-3, cleanly give rise to diastereomeric products, and thus the rhodium-catalyzed reaction is stereospecific. In addition, simple TADDOL-derived phenyl monophosphite ligands in combination with Rh(nbd)2BF 4 afford highly enantioselective catalysts (seven examples, 91-98% ee). These catalysts provide an alternative methodology to prepare Felkin or anti-Felkin acetate-aldol products and related derivatives that are obtainable from the intermediate chiral organoboranes. Copyright

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The present invention provides a method for producing optically active amines of formula (9) or (10): which comprises reacting an imine equivalent of formula (6): with an alkene of formula (7) or an alkyne of formula (8): in the presence of a chiral catalyst, which method does not require additional procedures such as introduction and removal of protecting groups and gives said amines with high purity and high operability.The optically active amines are useful as synthetic 15 intermediates for pharmaceuticals, agrochemicals, etc.

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Metal catalyst and ligand design,
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The direct, photoacid-catalyzed synthesis of 2-deoxyglycosides from glycals is reported. A series of phenol-conjugated acridinium-based organic photoacids were rationally designed, synthesized, and studied alongside the commercially available phenolic catalyst eosin Y. In the presence of such a photoacid catalyst and light, synthetic glycals were activated and coupled with a range of alcohols to afford 2-deoxyglycosides in good yields and with excellent alpha-selectivity.

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Phosphoroselenoyl chloride bearing a l,1?-bi-2-naphthyl group was reacted with racemic 2-alkanols to give the corresponding esters. Based on the multiple combination of their NMR spectra, a method for the assignment of the absolute configuration of 1 -aryl-2-propanols was established. The solidstate conformations of the esters were confirmed by X-ray structure analyses.

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In the past years, stereoselective functionalizations of hydroxyl groups of alcohol substrates with chlorosilanes leading to silyl ether formation have evolved from a functional-group protection to an enantioselective synthetic strategy. This work comprises a controlled desymmetrization of dichlorosilanes by using a family of structurally specific chiral diols, chiral 1,1?-binaphthalene-2-alpha-arylmethanol-2?-ol (Ar-BINMOL). This process led to the facile construction of silicon-stereogenic organosilicon compounds with high yields and good diastereoselectivities. In addition, the diasteroselective silylation of chiral diols might not only be of interest for the development of highly stereoselective nucleophilic silylation, but also shed light on the construction of novel chiral phosphine ligands bearing a silicon-stereogenic center.

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Two novel photo-responsive chiral cyclic molecular switches constituted of stiff stilbene and binaphthyl moieties connected through alkyl chains of different length were fabricated. The cyclization synthetic strategy employed herein made it convenient to obtain the pure Z isomers rather than Z/E isomer mixtures. The detailed photo-switching behaviors of target compounds were studied by the UV-Vis absorption and circular dichroism spectra in dichloromethane. The twist angles of the binaphthyl of the switches were able to be reversibly modulated by Z/E isomerization of stiff stilbene unit under alternative UV light stimuli and influenced by the length of alkyl chain to some extent.

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Metal catalyst and ligand design,
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A series of novel chiral diphosphite ligands have been synthesized from d-mannitol derivatives and chlorophosphoric acid diary ester, and were successfully employed in the copper catalyzed enantioselective conjugate addition of organozinc reagents diethylzinc and dimethylzinc to cyclic and acyclic enones. The stereochemically matched combination of d-mannitol and (R)-H8-binaphthyl in ligand 1,2:5,6-di-O-isopropylidene-3,4-bis[(R)- 1,1?-H8-binaphthyl-2,2?-diyl] phosphite-d-mannitol was essential to afford 93% ee for 3-ethylcyclohexanone, 92% ee for 3-ethylcyclopentanone, and 90% ee for 3-ethylcycloheptanone in toluene, using Cu(OTf)2 as a catalytic precursor. The results clearly indicated that the chiral organocopper reagent exhibited high enantioselectivies for cyclic enones bearing different ring sizes. As for the backbone of this type of ligand, it has been demonstrated that 1,2:5,6-di-O-isopropylidene-d-mannitol was more efficient than 1,2:5,6-di-O-cyclohexylidene-d-mannitol. The sense of the enantiodiscrimination was mainly determined by the configuration of the diaryl phosphite moieties in the 1,4-addition of cyclic enones.

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The first total synthesis of (+)-tricycloclavulone having a unique tricyclo[5,3,0,01,4]decane skeleton and six chiral centers was achieved in a highly stereoselective manner. It includes a catalytic enantioselective [2+2]-cycloaddition reaction using novel chiral copper catalyst, extremely effecting an intramolecular ester transfer reaction, and asymmetric reduction of the carbonyl group on the alpha-chain using Noyori’s chiral ruthenium catalyst. Copyright

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The allylnickel-catalyzed living coordination polymerization of an allene derivative possessing a homochiral substituent, (R)-2-allenyloxy-2?- (phenylcarbamoyloxy)-1,1?-binaphthyl (2), gave a chiral polymer which was found to have a single-handed helical conformation in solution of aprotic solvents such as chloroform and tetrahydrofuran on the basis of its circular dichroism (CD) spectra and specific rotation. The chiral higher-order conformation of the polymer was supposed to be stabilized by elongation of the repeating unit. That is, the CD spectra and the specific rotation of the polymer solution in aprotic solvents were found to be influence by the degree of polymerization until it reaches about 55. The temperature-independent and solvent-dependent nature of the CD spectra indicated that the chiral conformation of the polymer is stable at least in the range of 0-60C in tetrahydrofuran which disappears by addition of protic solvents such as methanol.

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(Graph Presented) Separation factors as high as 115 were observed for the chromatographic resolution of many alpha,alpha?-dihydroxybiaryls with a single chiral stationary phase made from readily available amino acid derivatives. The stationary phase works well for biphenyl-type compounds. It works extremely well for larger bis-aromatic compounds, such as binaphthyl-type compounds.

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