- Photo-induced phosphorus radical involved semipinacol rearrangement reaction: Highly synthesis of γ-oxo-phosphonates
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Hydroxyphosphoric acids display the unique biological activities, and they have some attractive prospects as clinical drug moleculars. Herein, a new approach for the synthesis of γ-oxo-phosphonates (the precursor of hydroxyphosphoric acid) has been established through the semipinacol rearrangement tactic involved the photo-induced phosphorus radical process. Most important, this transformation is avoid of the external oxidants, and occurs very well under the sunlight irradiation, meanwhile the γ-oxo-phosphonate was easily derivatized to obtain γ-hydroxyphosphoric acid, thus highlights the synthesis value of this method.
- Wang, Chunhai,Huang, Xiaoling,Liu, Xueting,Gao, Suqian,Zhao, Bin,Yang, Shangdong
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supporting information
p. 677 - 680
(2019/08/27)
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- Access to Optically Enriched α-Aryloxycarboxylic Esters via Carbene-Catalyzed Dynamic Kinetic Resolution and Transesterification
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Optically active α-aryloxycarboxylic acids and their derivatives are important functional molecules. Disclosed here is a carbene-catalyzed dynamic kinetic resolution and transesterification reaction for access to this class of molecules with up to 99% yields and 99:1 er values. Addition of a chiral carbene catalyst to the ester substrate leads to two diastereomeric azolium ester intermediates that can quickly epimerize to each other and thus allows for effective dynamic kinetic resolution to be realized. The optically enriched ester products from our reaction can be quickly transformed to chiral herbicides and other bioactive molecules.
- Liu, Bin,Song, Runjiang,Xu, Jun,Majhi, Pankaj Kumar,Yang, Xing,Yang, Song,Jin, Zhichao,Chi, Yonggui Robin
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supporting information
p. 3335 - 3338
(2020/04/30)
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- The cytochrome: C -cyclo[6]aramide complex as a supramolecular catalyst in methanol
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A hydrogen-bonded macrocycle, cyclo[6]aramide, was found to form a supramolecular complex with cytochrome c, which enables the solubilization of the heme protein in methanol. The supramolecular complexation was evidenced by UV-vis, CD, and Raman spectroscopic techniques via structural characterization. Computational simulation based on the DFT method reveals the presence of strong hydrogen bonds formed between the lysine residues exposed on the protein surface and the oxygen atoms residing in the cavity of cyclo[6]aramide apart from cation-π interactions. The resulting cytochrome c-cyclo[6]aramide 1 exhibited higher activities than unmodified cytochrome c in the oxidation of benzhydrol to benzophenone with hydrogen peroxide at low temperatures. The enhanced activity with lowering temperature up to -40 °C indicates that the complex can act as a "cold-active" synzyme. The results achieved here demonstrate the potential of hydrogen-bonded macrocycles in supramolecular chemistry for catalytic reactions via ligand-protein interactions.
- Pan, Wang,Mao, Lijun,Shi, Mingsong,Fu, Yonghong,Jiang, Xiaomin,Feng, Wen,He, Youzhou,Xu, Dingguo,Yuan, Lihua
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supporting information
p. 3857 - 3866
(2018/03/06)
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- Porphyrin-Based Air-Stable Helical Radicals
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Stable helical radicals are promising multi-functional molecules in light of intriguing magnetic and chiroptical properties. Attempts were made to extend diphenylmethyl-fused NiII porphyrin radical to helical system as the first air-stable orga
- Kato, Kenichi,Furukawa, Ko,Mori, Tadashi,Osuka, Atsuhiro
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supporting information
p. 572 - 575
(2018/01/26)
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- Catalysts, ligands and use thereof
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According to the present invention, there is provided a catalytic complex comprising a metal, one or more ligands and one or more counterions, wherein said one or more ligands include a non-racemic chiral ligand and wherein said one or more counterions include a triflimide counterion. Also provided are methods of making said catalytic complex and processes for producing chiral compounds which involve the use of said catalytic complex. In addition, the present invention provides compounds of the formula (2) as defined herein. The compounds of formula (2) may be useful as ligands in catalytic complexes.
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Page/Page column 70; 71
(2017/05/17)
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- Visible light-mediated arylalkylation of allylic alcohols through concomitant 1,2-aryl migration
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A photocatalytic process for selective arylalkylation of allylic alcohols with α-bromo diethyl malonate has been developed. The reaction provided a straightforward approach to synthesize α-aryl-β-alkylated ketones via unique 1,2-aryl migration. The procedure is highlighted by its operational simplicity and mild reaction conditions.
- Huang, Hong-Li,Yan, Hang,Yang, Chao,Xia, Wujiong
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supporting information
p. 4910 - 4913
(2015/03/18)
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- Recyclable and reusable Pd(OAc)2/P(1-Nap)3/[bmim][PF6]/H2O system for the addition of arylboronic acids to aldehydes
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A stable and efficient Pd(OAc)2/P(1-Nap)3[tri(1-naphthyl)phosphine] catalytic system for the addition of arylboronic acids to aldehydes has been developed. In the presence of Pd(OAc)2 and P(1-Nap)3, the addition reaction of arylboronic acids with aldehydes was carried out smoothly at 65 °C to give a variety of carbinol derivatives in good to excellent yields using a mixture of [bmim][PF6] and water as the solvent. The isolation of the products was readily performed by the extraction with diethyl ether, and the Pd(OAc)2/P(1-Nap)3/[bmim][PF6]/H2O system could be easily recycled and reused six times without significant loss of catalytic activity. Our system not only avoids the use of easily volatile THF or toluene as solvent but also solves the basic problem of palladium catalyst and these phosphine ligand reuse.
- Zhao, Hong,Cheng, Mingzhu,Zhang, Tinli,Cai, Mingzhong
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- UV light-mediated difunctionalization of alkenes through aroyl radical addition/1,4-/1,2-Aryl shift cascade reactions
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UV light-mediated difunctionalization of alkenes through an aroyl radical addition/1,4-/1,2-aryl shift has been described. The resulted aroyl radical from a photocleavage reaction added to acrylamide compounds followed by cyclization led to the formation of oxindoles, whereas the addition to cinnamic amides aroused a unique 1,4-aryl shift reaction. Furthermore, the difunctionalization of alkenes of prop-2-en-1-ols was also achieved through aroyl radical addition and a sequential 1,2-aryl shift cascade reaction.
- Zheng, Lewei,Huang, Hongli,Yang, Chao,Xia, Wujiong
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supporting information
p. 1034 - 1037
(2015/03/30)
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- Efficient 1,2-addition of aryl- and alkenylboronic acids to aldehydes catalyzed by the palladium/thioether-imidazolinium chloride system
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(Chemical Equation Presented) The high level of catalyst performance was attainable in the palladium-catalyzed 1,2-addition of aryl-, heteroaryl-, and alkenylboronic acids to aromatic, heteroaromatic, and aliphatic aldehydes using thioether-imidazolinium chloride L5 as a heterobidentate carbene ligand precursor.
- Kuriyama, Masami,Shimazawa, Rumiko,Shirai, Ryuichi
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p. 1597 - 1600
(2008/09/17)
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- The palladium-catalyzed addition of aryl- and heteroarylboronic acids to aldehydes
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(Chemical Equation Presented) Reaction of aryl- or heteroarylboronic acids with aldehydes, in the presence of PdCl2 and P(1-Nap)3, afforded carbinol derivatives in good to excellent yields. The efficiency of this reaction was demonstrated by the compatibility with nitro, cyano, acetamido, acetoxy, acetyl, carboxyl, trifluoromethyl, fluoro, and chloro groups and the possibility of involving aliphatic aldehyde or hindered substrates. Moreover, the rigorous exclusion of air/moisture is not required in these transformations.
- Qin, Changming,Wu, Huayue,Cheng, Jiang,Chen, Xi'an,Liu, Miaochang,Zhang, Weiwei,Su, Weike,Ding, Jinchang
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p. 4102 - 4107
(2008/02/04)
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- Complete chiral induction from enantiopure 1,2-diamines to benzophenone-based achiral bisphosphane ligands in noyori-type RuII catalysts
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We report the design and synthesis of a novel class of RuII catalysts (3) composed of achiral benzophenone-based bisphosphane ligands and enantiopure 1,2-diamines for the asymmetric hydrogenation of aryl ketones. The developed catalysts show excellent enantioselectivities (up to 97 % ee) and activities (up to S/C = 10,000) in the hydrogenation of a variety of aromatic ketones. Complete chiral induction from the enantiopure 1,2-diamine to the achiral bisphosphane ligand was observed. The coordination of the C=O moiety in 3 to the cationic RuII center is considered to be of key importance in providing a higher thermodynamic and kinetic rotation barrier for the flexible bisphosphane ligand, resulting in the preferential formation of only one diastereomer, and thus explaining the high enantioselectivity of the catalyst. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Jing, Qing,Sandoval, Christian A.,Wang, Zheng,Ding, Kuiling
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p. 3606 - 3616
(2012/12/23)
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- Reactions of Bis(2,6-dimethoxyphenyl)methanol in Common Organic Solvents in the Presence of an Acid
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The title compound, Φ2CHOH [Φ = 2,6-(MeO)2C6H3] (1), reacted in acetone under mild conditions in the presence of acid to give a new ketone, Φ2CHCH2COMe. Analogous reactions were observed in
- Wada, Masanori,Konishi, Hideki,Kai, Takanori,Takeuchi, Hiroshi,Natsume, Satoko,Erabi, Tatsuo
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p. 1667 - 1672
(2007/10/03)
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- Molecular conformation of di-o-anisylcarbinol: an X-ray diffraction study
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Di-o-anisylcarbinol crystallizes in the triclinic system, space group P1 with a=7.50(4), b=10.89(4), c=7.98(3) Angstroem, α=101(9), β=94.1(1), γ=94.6(1) deg, Z=2, V=633.11 Angstroem 3, Dx=1.28 mg m-3, Dm=1.26(1) mg m-3, CuKα radiation, λ=1.54178 Angstroem, μ(CuKα)=0.633 mm-1, F(000)=260.The structure has been determined by direct methods using single crystal X-ray data and refined by least-squares to the final R factors R=5.89percent and Rw=5.35percent.The molecule has a twist-skewed conformation with the phenyl rings on nearly orthogonal planes.The crystal structure shows a hydrogen-bonded dimer and a peculiar arrangement of the methoxy and phenyl groups.
- Faerman, C.,Negri, H.,Punte, G.,Vitale, A. A.,Nudelman, N. S.
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p. 2001 - 2005
(2007/10/02)
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