- Novel σ1 antagonists designed for tumor therapy: Structure – activity relationships of aminoethyl substituted cyclohexanes
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Depending on the substitution pattern and stereochemistry, 1,3-dioxanes 1 with an aminoethyl moiety in 4-position represent potent σ1 receptor antagonists. In order to increase the stability, a cyclohexane ring first replaced the acetalic 1, 3-dioxane ring of 1. A large set of aminoethyl substituted cyclohexane derivatives was prepared in a six-step synthesis. All enantiomers and diastereomers were separated by chiral HPLC at the stage of the primary alcohol 7, and their absolute configuration was determined by CD spectroscopy. Neither the relative nor the absolute configuration had a large impact on the σ1 affinity. The highest σ1 affinity was found for cis-configured benzylamines (1R,3S)-11 (Ki = 0.61 nM) and (1S,3R)-11 (Ki = 1.3 nM). Molecular dynamics simulations showed that binding of (1R,3S)-11 at the σ1 receptor is stabilized by the typical polar interaction of the protonated amino moiety with the carboxy group of E172 which is optimally oriented by an H-bond interaction with Y103. The lipophilic interaction of I124 with the N-substituent also contributes to the high σ1 affinity of the benzylamines. The antagonistic activity was determined in a Ca2+ influx assay in retinal ganglion cells. The enantiomeric cis-configured benzylamines (1R,3S)-11 and (1S,3R)-11 were able to inhibit the growth of DU145 cells, a highly aggressive human prostate tumor cell line. Moreover, cis-11 could also inhibit the growth of further human tumor cells expressing σ1 receptors. The experimentally determined logD7.4 value of 3.13 for (1R,3S)-11 is in a promising range regarding membrane penetration. After incubation with mouse liver microsomes and NADPH for 90 min, 43% of the parent (1R,3S)-11 remained unchanged, indicating intermediate metabolic stability. Altogether, nine metabolites including one glutathione adduct were detected by means of LC-MS analysis.
- Kopp, Nicole,Holtschulte, Catharina,B?rgel, Frederik,Lehmkuhl, Kirstin,Friedland, Kristina,Civenni, Gianluca,Laurini, Erik,Catapano, Carlo V.,Pricl, Sabrina,Humpf, Hans-Ulrich,Schepmann, Dirk,Wünsch, Bernhard
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- Synthesis, structure, and function of pcp pincer transition-metal-complex- bound norvaline derivatives
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A PCP pincer palladium-complex-bound norvaline, Boc-l-[Pd]Nva-OMe, was synthesized and fully characterized by NMR, FT-ICR-MS, and X-ray crystallography. Selective N- and C-terminus transformations of Boc-l-[Pd]Nva-OMe were performed by conventional deprotection-condensation procedures to afford lipophilic palladium-bound norvaline derivatives without metal detachment. The N-/C-bisfunctionalized palladium-bound norvaline showed self-assembly properties, as evidenced by supramolecular gel formation. The catalytic activity of the supramolecular gel was assessed in the 1,4-conjugate addition of phenylboronic acid.
- Takaya, Hikaru,Iwaya, Takashi,Ogata, Kazuki,Isozaki, Katsuhiro,Yokoi, Tomoya,Yoshida, Ryota,Yasuda, Nobuhiro,Seike, Hirofumi,Takenaka, Toshio,Nakamura, Masaharu
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- Phosphine-olefin ligands: A facile dehydrogenative route to catalytically active rhodium complexes
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Facile, metal-mediated, (acceptorless) dehydrogenation of tricyclopentyl phosphine directly affords rhodium chelating phosphine-olefin complexes, some of which are catalytically active for 1,4-additions. The Royal Society of Chemistry 2006.
- Douglas, Thomas M.,Notre, Jerome Le,Brayshaw, Simon K.,Frost, Christopher G.,Weller, Andrew S.
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- Radical cyclizations of 2-(ω-haloalkylthio)enones to thiapolycycloalkanones
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Radical cyclization of 2-(ω-haloalkylthio)enones gives predominantly fused-thiapolycycloalkanones. (C) 2000 Elsevier Science Ltd.
- Ponaras, Anthony A.,Zaim, ?mer
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- Synthesis of β-Selenylated Cyclopentanones via Photoredox-Catalyzed Selenylation/Ring-Expansion Cascades of Alkenyl Cyclobutanols
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A photoredox strategy to access β-selenated cyclic ketone derivatives through the coupling reaction of 1-(1-arylvinyl)cyclobutanols with diselenides under blue LED irradiation and an air atmosphere was developed. This reaction employs the easily accessibl
- Jung, Hye Im,Kim, Dae Young
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- Asymmetric Induction with Amidocuprates
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Optically active amines such as (R)- or (S)-α-methylbenzylamine and (4S,5S)-(+)-5-amino-2,2-dimethyl-4-phenyl-1,3-dioxane can be lithiated with an alkyllithium an added to an organocopper(I) compound, prepared from a lithium reagent and CuI, to give a chi
- Bertz, Steven H.,Dabbagh, Gary,Sundararajan, G.
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- MORE HIGHLY MIXED, HIGHER ORDER CYANOCUPRATES "rt(2-thienyl)Cu(CN)Li2". EFFICIENT REAGENTS WHICH PROMOTE SELECTIVE LIGAND TRANSFER
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The combination of an organolithium (RTLi) and 2-lithiothiophene (2-thienyl) with CuCN forms a new reagents, "RT(2-thienyl)Cu(CN)Li2".This species selectively transfers the RT ligand in substitution reactions with epoxides and halides.In conjugate addition processes, the cuprate reacts with unhindered substrates, while β,β-disubstituted cases unexpectedly afford products resulting from 1,2-addition of the thiophene group.The prospects for use of these reagents in the synthesis of polyene macrolide antibiotics are discussed.
- Lipshutz, Bruce H.,Kozlowski, Joseph A.,Parker, David A.,Nguyen, Sam L.,McCarthy, Keith E.
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- Synthesis of dibromobenzobarrelene derivatives and catalytic activity of their rhodium complexes
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A novel synthetic route based on [4+2] cycloaddition for dibromobenzobarrelene derivatives starting from in situ generated 3,5-dibromo-1,2-didehydrobenzene and mesitylene, 1,2,4,5-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, pentamethylbenzene, 1,3-dimethoxybenzene, and 2,4,6-trimethylbromobenzene, respectively, was developed. Thus, six novel dibromobenzobarrelenes with diverse substitution patterns at the barrelene framework including chiral derivatives are reported. The benzobarrelene 6,8-dibromo-1,3,10-trimethyl-1,4-dihydro-1,4-ethenonaphthalene (1a) was functionalized at the annulated benzene ring to give three novel carboxylic acids and two novel phosphonic acid esters. Selected benzobarrelene complexes with RhICl were tested for their catalytic activity in the 1,4-addition of phenylboronic acid towards cyclohex-2-enone. Turnover frequencies up to 3405 h-1 were observed, which are among the highest reported so far for Rh-diene complexes in this type of C-C coupling reaction. The synthesis by means of a [4+2] cycloaddition approach of six novel dibromobenzobarrelenes with diverse substitution patterns at the barrelene framework, including chiral derivatives, is reported as well as the functionalization of 6,8-dibromo-1,3,10-trimethyl-1,4-dihydro-1,4- ethenonaphthalene to give carboxylic acid and phosphonic acid ester derivatives. Copyright
- Schlesinger, Maik,Hofmann, Max,Rueffer, Tobias,Schaarschmidt, Dieter,Lang, Heinrich,Theilacker, Sergio,Schuermann, Markus,Jurkschat, Klaus,Mehring, Michael
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- Detailed Structural Analysis of a Self-Assembled Vesicular Amphiphilic NCN-Pincer Palladium Complex by Using Wide-Angle X-Ray Scattering and Molecular Dynamics Calculations
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Wide-angle X-ray scattering experiments and all-atomistic molecular dynamics calculations were performed to elucidate the detailed structure of bilayer vesicles constructed by self-assembly of an amphiphilic palladium NCN-pincer complex. We found an excel
- Hamasaka, Go,Muto, Tsubasa,Andoh, Yoshimichi,Fujimoto, Kazushi,Kato, Kenichi,Takata, Masaki,Okazaki, Susumu,Uozumi, Yasuhiro
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- Fine-Tuning the Bicyclo[3.3.1]nona-2,6-diene Ligands: Second Generation 4,8-Substituted Dienes for Rh-Catalyzed Asymmetric 1,4-Addition Reactions
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Design and synthesis of the second generation C2-symmetric 4,8-endo,endo-bis(alkoxy) bicyclo[3.3.1]nona-2,6-diene ligands possessing additional 4,8-exo,exo substituents is reported. The 4,8-exo,exo groups provide a further element for fine-tuning of the ligand structure by enforcing conformational rigidity of the 4,8-endo,endo side chains. Such tetrasubstituted bicyclo[3.3.1]nona-2,6-dienes were employed as steering ligands in the rhodium-catalyzed arylation of cyclic enones with arylboronic acids, providing the corresponding 1,4-addition products in good to excellent yields (69–99 %) and enantioselectivities up to 99 % ee.
- Bieliūnas, Vidmantas,Ston?ius, Sigitas
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p. 3815 - 3823
(2021/07/28)
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- C1-Symmetric Binap Derivative Featuring Single Diferrocenylphosphino-Donor Moiety
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A C1-symmetric chiral bisphosphine, FcPh-Binap (1), which possesses a single diferrocenylphosphino moiety together with a conventional Ph2P-substituent, was prepared in enantiomerically pure forms. Ligand 1 is sterically less demanding than Fc-Segphos (A)
- Enomoto, Yuuki,Ichiryu, Hiroki,Hu, Hao,Ura, Yasuyuki,Ogasawara, Masamichi
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supporting information
p. 1020 - 1024
(2021/05/07)
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- Enantioselective Reductive Homocoupling of Allylic Acetates Enabled by Dual Photoredox/Palladium Catalysis: Access to C2-Symmetrical 1,5-Dienes
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Transition-metal-catalyzed reductive coupling reactions have emerged as powerful protocols to construct C-C bonds. However, the development of enantioselective C(sp3)-C(sp3) reductive coupling remains challenging. Herein, we report a highly regio-, diastereo-, and enantioselective reductive homocoupling of allylic acetates through cooperative palladium and photoredox catalysis using diisopropylethylamine or Hantzsch ester as a homogeneous organic reductant. This straightforward protocol enables the stereoselective construction of C(sp3)-C(sp3) bonds under mild reaction conditions. A series of C2-symmetrical chiral 1,5-dienes were easily prepared with excellent enantioselectivities (up to >99% ee), diastereoselectivities (up to >95:5 dr), and regioselectivities (up to >95:5 rr). The resultant chiral 1,5-dienes can be directly used as chiral ligands in asymmetric synthesis, and they can be also transformed into other valuable chiral ligands.
- Zhang, Hong-Hao,Tang, Menghan,Zhao, Jia-Jia,Song, Changhua,Yu, Shouyun
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supporting information
p. 12836 - 12846
(2021/08/30)
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- Enantioselective Hydrogenation of Endocyclic Enones: the Solution to a Historical Problem?
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The enantioselective hydrogenation of endocyclic enones has been a historical problem for homogeneous catalysis. We herein report an efficient method to reduce endocyclic enones with molecular hydrogen. Catalyzed by a rhodium/Zhaophos complex, a variety of enones with five-, six- or seven-member ring were hydrogenated with high enantioselectivity (92%—99% ee). Excellent chemo- and enantioselectivity demonstrated this method was successfully applied in the enantioselective hydrogenation of citral to produce enantio-enriched citronellal.
- Lang, Qiwei,Yang, Huaxin,Gu, Guoxian,Feng, Qiang,Wen, Jialin,Zhang, Xumu
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p. 933 - 936
(2021/03/03)
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- Enantioselective Conjugate Addition of Stabilized Arylzinc Iodide to Enones: an Improved Protocol of the Hayashi Reaction
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Stabilised arylzinc iodide, prepared by direct insertion of zinc into aryl iodides, were used as nucleophiles in the Hayashi Rh-catalysed enantioselective conjugate addition to enones. The reaction conditions were optimized in the addition of phenylzinc i
- Casotti, Gianluca,Rositano, Vincenzo,Iuliano, Anna
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p. 1126 - 1131
(2020/12/17)
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- Carbonyl 1,2-transposition through triflate-mediated a-amination
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To date, it remains challenging to selectively migrate a carbonyl oxygen within a given molecular scaffold, especially to an adjacent carbon. In this work, we describe a simple one- or two-pot protocol that transposes a ketone to the vicinal carbon. This approach first converts the ketone to the corresponding alkenyl triflate, which can then undergo the palladium- and norbornene-catalyzed regioselective a-amination and ipso-hydrogenation enabled by a bifunctional hydrogen and nitrogen donor. The resulting "transposed enamine" intermediate can subsequently be hydrolyzed to produce the 1,2-carbonyl-migrated product. This method allows rapid access to unusual bioactive analogs through late-stage functionalization.
- Wu, Zhao,Xu, Xiaolong,Wang, Jianchun,Dong, Guangbin
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p. 734 - 740
(2021/11/16)
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- Deciphering Reactivity and Selectivity Patterns in Aliphatic C-H Bond Oxygenation of Cyclopentane and Cyclohexane Derivatives
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A kinetic, product, and computational study on the reactions of the cumyloxyl radical with monosubstituted cyclopentanes and cyclohexanes has been carried out. HAT rates, site-selectivities for C-H bond oxidation, and DFT computations provide quantitative information and theoretical models to explain the observed patterns. Cyclopentanes functionalize predominantly at C-1, and tertiary C-H bond activation barriers decrease on going from methyl- and tert-butylcyclopentane to phenylcyclopentane, in line with the computed C-H BDEs. With cyclohexanes, the relative importance of HAT from C-1 decreases on going from methyl- and phenylcyclohexane to ethyl-, isopropyl-, and tert-butylcyclohexane. Deactivation is also observed at C-2 with site-selectivity that progressively shifts to C-3 and C-4 with increasing substituent steric bulk. The site-selectivities observed in the corresponding oxidations promoted by ethyl(trifluoromethyl)dioxirane support this mechanistic picture. Comparison of these results with those obtained previously for C-H bond azidation and functionalizations promoted by the PINO radical of phenyl and tert-butylcyclohexane, together with new calculations, provides a mechanistic framework for understanding C-H bond functionalization of cycloalkanes. The nature of the HAT reagent, C-H bond strengths, and torsional effects are important determinants of site-selectivity, with the latter effects that play a major role in the reactions of oxygen-centered HAT reagents with monosubstituted cyclohexanes.
- Martin, Teo,Galeotti, Marco,Salamone, Michela,Liu, Fengjiao,Yu, Yanmin,Duan, Meng,Houk,Bietti, Massimo
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supporting information
p. 9925 - 9937
(2021/06/30)
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- Ir(NHC)-Catalyzed Synthesis of β-Alkylated Alcohols via Borrowing Hydrogen Strategy: Influence of Bimetallic Structure
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Multi N-heterocyclic carbene(NHC)-modified iridium catalysts were employed in the β-alkylation of alcohols; dimerization of primary alcohols (Guerbet reaction), cross-coupling of secondary and primary alcohols, and intramolecular cyclization of alcohols. Mechanistic studies of Guerbet reaction, including kinetic experiments, mass analysis, and density functional theory (DFT) calculation, were employed to explain the fast reaction promoted by bimetallic catalysts, and the dramatic reactivity increase of monometallic catalysts at the late stage of the reaction. (Figure presented.).
- Sung, Kihyuk,Lee, Mi-hyun,Cheong, Yeon-Joo,Kim, Yu Kwon,Yu, Sungju,Jang, Hye-Young
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p. 3090 - 3097
(2021/05/10)
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- Low-Temperature Intramolecular [4+2] Cycloaddition of Allenes with Arenes for the Synthesis of Diene Ligands
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The intramolecular [4+2] cycloaddition between arenes and allenes first reported by Himbert gives rapid access to rigid polycyclic scaffolds. Herein, we report a one-pot oxyalkynylation/cycloaddition reaction proceeding under mild conditions (23–90 °C) an
- Hari, Durga Prasad,Pisella, Guillaume,Wodrich, Matthew D.,Tsymbal, Artem V.,Tirani, Farzaneh Fadaei,Scopelliti, Rosario,Waser, Jerome
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supporting information
p. 5475 - 5481
(2021/01/21)
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- Organic Solvent-free Asymmetric 1,4-Addition in Liquid- or Solid-State using Conventional Stirring Catalyzed by a Chiral Rhodium Complex Developed as a Homogeneous Catalyst
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Organic solvent-free asymmetric 1,4-addition of arylboronic acids to enone substrates was performed by using a chiral rhodium complex catalyst developed as a homogeneous catalyst. Reactions catalyzed by [RhOH(cod)]2 with chiral diphosphine ligands in liquid- or solid-state proceeded to give chiral 1,4-adducts in high yield with enantioselectivities up to ca. 100 % ee by conventional stirring without mechanochemistry such as ball milling. The solid-state reactions under a static condition also proceeded, but with a slight decrease in enantioselectivity of the 1,4-adduct. SEM observations of the solid-state reactions indicated that no nanoparticles catalyst was generated. The organic solvent-free reaction could be applied to gram-scale synthesis by performing a greener purification using a minimum necessary organic solvent.
- Korenaga, Toshinobu,Kori, Hiroto,Asai, Shota,Kowata, Ryo,Shirai, Masayuki
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p. 6059 - 6066
(2020/10/28)
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- Synthesis, Characterization, and Application of Segphos Derivative Having Diferrocenylphosphino-Donor Moieties
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An axially chiral bisphosphine, Fc-Segphos (1), which possesses diferrocenylphosphino-donor moieties, was prepared as a racemate, and its optical resolution was achieved by the use of chiral HPLC. Ligand 1 coordinated to a palladium(II) cation in a bidentate fashion to construct a unique chiral environment at the palladium center due to the sterically demanding ferrocenyl groups. Ligand (R)-1 was applied in the palladium-catalyzed asymmetric synthesis of axially chiral allenes showing good enantioselectivity of up to 92% ee. In general, (R)-1 displayed better enantioselectivity than the parent Segphos in the palladium-catalyzed reaction, and the Pd/(R)-1 species showed up to 18% ee enhancement over the (R)-Segphos-derived palladium catalyst.
- Hu, Hao,Ichiryu, Hiroki,Nakajima, Kiyohiko,Ogasawara, Masamichi,Ohki, Yasuhiro,Seki, Naoki
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- trans-Cyclooctenes as Chiral Ligands in Rhodium-Catalyzed Asymmetric 1,4-Additions
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trans-Cyclooctenes serve as asymmetric ligands for the rhodium-catalyzed 1,4-additions of organotin reagents to enones. We demonstrate, for the first time, that these chiral olefins can provide efficient coordination spheres for asymmetric metal catalysis. As the asymmetric environment around the reaction site is constructed by the trans-cyclooctene framework, the introduction of a substituent at the allylic position further improves enantioselectivity to 93 % ee. These findings provide new chiral framework designs for the asymmetric ligands of metal catalysts.
- Nagano, Tagui,Einaru, Shunsuke,Shitamichi, Kenta,Asano, Keisuke,Matsubara, Seijiro
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supporting information
p. 7131 - 7133
(2020/09/11)
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- Counterion Enhanced Organocatalysis: A Novel Approach for the Asymmetric Transfer Hydrogenation of Enones
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We present a novel strategy for organocatalytic transfer hydrogenations relying on an ion-paired catalyst of natural l-amino acids as main source of chirality in combination with racemic, atropisomeric phosphoric acids as counteranion. The combination of a chiral cation with a structurally flexible anion resulted in a novel chiral framework for asymmetric transfer hydrogenations with enhanced selectivity through synergistic effects. The optimized catalytic system, in combination with a Hantzsch ester as hydrogen source for biomimetic transfer hydrogenation, enabled high enantioselectivity and excellent yields for a series of α,β-unsaturated cyclohexenones under mild conditions. Moreover, owing to the use of readily available and chiral pool-derived building blocks, it could be prepared in a straightforward and significantly cheaper way compared to the current state of the art.
- Scharinger, Fabian,Márk Pálv?lgyi, ádám,Zeindlhofer, Veronika,Schnürch, Michael,Schr?der, Christian,Bica-Schr?der, Katharina
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p. 3776 - 3782
(2020/06/22)
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- The synthesis method of one-carbon ring expansion of cycloketone dericatives from β-selenyl cycloketone dericatives
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The present invention relates to a method for preparing a cyclic ketone derivative with an increased carbon number by performing a ring expansion reaction of a β-selenyl cyclic ketone derivative. The present invention was first developed by performing the
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Paragraph 0041; 0044-0048
(2020/09/08)
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- BISPHOSPHINOHEXAFLUOROCYCLOPENTENE DERIVATIVE, MANUFACTURING METHOD THEREOF, TRANSITION METAL COMPLEX, AND ORGANIC COMPOUND MANUFACTURING METHOD BASED ON THE SAME
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PROBLEM TO BE SOLVED: To provide an asymmetric catalyst allowing synthesis of an organic compound having appealing properties absent in existing organic compounds. SOLUTION: The invention provides an asymmetric catalyst comprising a transition metal compl
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Paragraph 0186-0189
(2020/08/29)
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- Synthesis of multinuclear Rh(I) complexes bearing triazolylidenes and their application in C-C and c-Si bond forming reactions
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Multidentate carbene ligands are valuable frameworks for the preparation of carbene complexes displaying higher nuclearity. In the present work, we report the synthesis of a series of mono- to tetra-[Rh(COD)I] complexes (3a- d) supported by mesoionic triazol-5-ylidenes. The general synthetic procedure involves the one step reaction of the appropriate triazolium (2a-d) salt in the presence of KHMDS and stoiquiometric amounts of the rhodium(I) precursor. Treatment of complexes 3a-d with an excess of carbon monoxide allows for the quantitative preparation of complexes 4a-d featuring a [Rh(CO)2I] fragment used for the detemination of the donor properties of the new triazolylidene ligands. All complexes have been fully characterized by means of 1H and 13C NMR spectroscopy, melting point, elemental analysis, and in the case of complex 3a, by X-ray crystallography. Comparison of the catalytic activity of the new rhodium complexes in C-C and C-Si bond forming processes demonstrate the enhanced performance of the tetranuclear species suggesting the possibility of strong cooperative effects in these multinuclear complexes.
- Mendoza-Espinosa, Daniel,Rendón-Nava, David,Vásquez-Pérez, Jose M.,Sandoval-Chávez, Cesar I.,Alvarez-Hernández, Alejandro
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supporting information
p. 3961 - 3971
(2020/12/01)
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- Arylation of indoles using cyclohexanones dually-catalyzed by niobic acid and palladium-on-carbons
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3-Arylindoles were easily constructed from indoles and cyclohexanone derivatives using a combination of catalytic niobic acid-on-carbon (Nb2O5/C) and palladium-on-carbon (Pd/C) under heating conditions without any oxidants. The Lewis acidic Nb2O5/C promoted the nucleophilic addition of indoles to the cyclohexanones, and the subsequent dehydration and Pd/C-catalyzed dehydrogenation produced the 3-arylindoles. The additive 2,3-dimethyl-1,3-butadiene worked as a hydrogen acceptor to facilitate the dehydrogenation step.
- Ban, Kazuho,Sajiki, Hironao,Sawama, Yoshinari,Yamamoto, Yuta
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supporting information
p. 3898 - 3902
(2020/06/03)
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- Enantioselective Synthesis of Atropisomeric Anilides via Pd(II)-Catalyzed Asymmetric C-H Olefination
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Atropisomeric anilides have received tremendous attention as a novel class of chiral compounds possessing restricted rotation around an N-aryl chiral axis. However, in sharp contrast to the well-studied synthesis of biaryl atropisomers, the catalytic asym
- Yao, Qi-Jun,Xie, Pei-Pei,Wu, Yong-Jie,Feng, Ya-Lan,Teng, Ming-Ya,Hong, Xin,Shi, Bing-Feng
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supporting information
p. 18266 - 18276
(2020/11/02)
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- Heterogeneous Chiral Diene-Rh Complexes for Asymmetric Arylation of α,β-Unsaturated Carbonyl Compounds, Nitroalkenes, and Imines
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A chiral diene ligand with tertiary alkyl amine-derived secondary amide moiety was immobilized on cross-linked polystyrene (PS) by radical polymerization, which was combined with Rh to form heterogeneous chiral Rh complexes (PS-diene Rh?Cl). PS-diene Rh?Cl catalyzed asymmetric arylation reactions of α,β-unsaturated carbonyl compounds (ketones, esters, and amides), nitroalkenes, and imines afforded the desired products in high yields with excellent enantioselectivities. PS-diene Rh?Cl is stable in air, can be stored for several months, and can be reused more than 10 times without any reduction of either yield or enantioselectivity. We also developed a method of activation of PS-diene Rh?Cl to generate more active species. (Figure presented.).
- Kuremoto, Tatsuya,Yasukawa, Tomohiro,Kobayashi, Shū
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supporting information
p. 3698 - 3703
(2019/07/12)
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- Heterogeneous Rh and Rh/Ag bimetallic nanoparticle catalysts immobilized on chiral polymers
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The development of heterogeneous chiral catalysts has lagged far behind that of homogeneous chiral catalysts in spite of their advantages, such as environmental friendliness for a sustainable society. We describe herein novel heterogeneous chiral Rh and Rh/Ag bimetallic nanoparticle catalysts consisting of polystyrene-based polymers with chiral diene moieties. The catalysts enable high-to-excellent yields and enantioselectivities to be obtained in asymmetric 1,4-addition reactions of arylboronic acids with α,β-unsaturated carbonyl compounds such as ketones, esters, and amides, and in other asymmetric reactions. The catalysts could be readily recovered by simple filtration and reused; they could also be applied to continuous-flow synthesis. We also discuss the nature of possible reaction species based on XPS analysis.
- Min, Hyemin,Miyamura, Hiroyuki,Yasukawa, Tomohiro,Kobayashi, Shu
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p. 7619 - 7626
(2019/08/20)
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- Steric Tuning of Sulfinamide/Sulfoxides as Chiral Ligands with C1, Pseudo-meso, and Pseudo-C2 Symmetries: Application in Rhodium(I)-Mediated Arylation
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A new family of sulfinamide/sulfoxide derivatives was synthesized as chiral bidentate ligands by stereoselective additions of methylsulfinyl carbanions to N-tert-butylsulfinylimines. The new ligands, with C1, pseudo-meso, and pseudo-C2 symmetries, were successfully assayed in Rh-catalyzed additions of arylboronic acids to activated ketones. The sterically dissymmetric C1 ligand (RS,SC,RS)-N-[1-(phenylsulfinyl)-3-methylbut-2-yl] tert-butylsulfinamide turned out to be the optimal one, allowing the 1,4-additions of diverse arylboronic acids, on different α,β-unsaturated cyclic ketones with high chemical yields and enantioselectivities up to >99% ee.
- Borrego, Lorenzo G.,Recio, Rocío,álvarez, Eleuterio,Sánchez-Coronilla, Antonio,Khiar, Noureddine,Fernández, Inmaculada
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supporting information
p. 6513 - 6518
(2019/08/20)
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- Enantioselective Conjugate Addition of Aryl Halides and Triflates to Electron-Deficient Olefins via Nickel- And Rhodium-Catalyzed Sequential Relay Reactions
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Asymmetric conjugate addition of aryl halides or aryl triflates to electron-deficient olefins was realized by sequential Miyaura borylation and Hayashi-Miyaura conjugate addition in one pot. A nickel-catalyzed borylation of aryl halides or triflates and a rhodium-chiral diene complex catalyzed enantioselective conjugate addition was executed as a pair of relay reactions as a more efficient and greener protocol.
- Fan, Chenrui,Wu, Qixu,Zhu, Chengfeng,Wu, Xiang,Li, Yougui,Luo, Yunfei,He, Jian-Bo
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supporting information
p. 8888 - 8892
(2019/10/14)
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- Asymmetric Baeyer-Villiger oxidation: Classical and parallel kinetic resolution of 3-substituted cyclohexanones and desymmetrization of: Meso -disubstituted cycloketones
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Regioselectivity is a crucial issue in Baeyer-Villiger (BV) oxidation. To date, few reports have addressed asymmetric BV oxidation of 3-substituted cycloketones due to the high difficulty of controlling regio- and stereoselectivity. Herein, we report the asymmetric BV oxidation of 3-substituted and meso-disubstituted cycloketones with chiral N,N′-dioxide/Sc(iii) catalysts performed in three ways: classical kinetic resolution, parallel kinetic resolution and desymmetrization. The methodology was applied in the total and formal synthesis of bioactive compounds and natural products. Control experiments and calculations demonstrated that flexible and adjustable catalysts played a significant role in the chiral recognition of substrates.
- Wu, Wangbin,Cao, Weidi,Hu, Linfeng,Su, Zhishan,Liu, Xiaohua,Feng, Xiaoming
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p. 7003 - 7008
(2019/07/31)
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- C-H Functionalization Approach for the Synthesis of Chiral C2-Symmetric 1,5-Cyclooctadiene Ligands
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Chiral cyclooctadiene (COD) derivatives are readily prepared by rhodium-catalyzed allylic C-H functionalization of COD. Either mono- or difunctionalization of COD is possible generating the products in high yield, diastereoselectivity and enantioselectivi
- Zhang, Bowen,Hollerbach, Michael R.,Blakey, Simon B.,Davies, Huw M. L.
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supporting information
p. 9864 - 9868
(2019/12/24)
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- Electrochemical Radical Selenylation/1,2-Carbon Migration and Dowd-Beckwith-Type Ring-Expansion Sequences of Alkenylcyclobutanols
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Electrochemical oxidative radical selenylation/1,2-carbon migration and Dowd-Beckwith-type ring-expansion sequences of alkenylcyclobutanols were developed in this study. This approach is environmentally benign and uses shelf-stable diselenides as selenium
- Kim, Yeon Joo,Kim, Dae Young
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p. 1021 - 1025
(2019/02/14)
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- Rh-catalyzed 1,4-addition reactions of arylboronic acids accelerated by co-immobilized tertiary amine in silica mesopores
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Mesoporous silica-supported Rh complex catalysts were prepared by simple silane-coupling, followed by complexation, and characterized by FT-IR, SEM, Rh K-edge XAFS, and elemental analysis. Local structures of the Rh complexes in each sample were almost similar to those of a nonporous silica-supported diaminorhodium complex. Co-immobilization of a tertiary amine on the same silica surface induced slight changes to the Rh complex structure in the case of the support with smaller pores. The prepared catalysts showed high activity for the 1,4-addition reaction of phenylboronic acids. Co-immobilization of the tertiary amine increased the reaction rate by more than 7-fold, with turnover number of nearly 8500. The catalytic performance achieved with this novel system is with much higher than that reported previously with a nonporous silica-supported catalyst. The mesoporous silica-supported Rh complex-tertiary amine showed a wide substrate scope, including unsaturated ketones and nitriles. This co-immobilized tertiary amine may activate phenylboronic acid to enhance its reactivity in the transmetalation step with Rh-OH species.
- Motokura, Ken,Hashiguchi, Kohei,Maeda, Kyogo,Nambo, Masayuki,Manaka, Yuichi,Chun, Wang-Jae
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- A consecutive process for C-C and C-N bond formation with high enantio-and diastereo-control: Direct reductive amination of chiral ketones using hydrogenation catalysts
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High diastereoselectivity was observed in the Rh-catalysed reductive amination of 3-arylcyclohexanones to form tertiary amines. This was incorporated into a one-pot enantioselective conjugate addition and diastereoselective reductive amination, including an example of assisted tandem catalysis.
- Gilbert, Sophie H.,Viseur, Virginie,Clarke, Matthew L.
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supporting information
p. 6409 - 6412
(2019/06/07)
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- Selective Synthesis of Primary Anilines from NH3 and Cyclohexanones by Utilizing Preferential Adsorption of Styrene on the Pd Nanoparticle Surface
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Dehydrogenative aromatization is one of the attractive alternative methods for directly synthesizing primary anilines from NH3 and cyclohexanones. However, the selective synthesis of primary anilines is quite difficult because the desired primary aniline products and the cyclohexanone substrates readily undergo condensation affording the corresponding imines (i.e., N-cyclohexylidene-anilines), followed by hydrogenation to produce N-cyclohexylanilines as the major products. In this study, primary anilines were selectively synthesized in the presence of supported Pd nanoparticle catalysts (e.g., Pd/HAP, HAP=hydroxyapatite, Ca10(PO4)6(OH)2) by utilizing competitive adsorption unique to heterogeneous catalysis; in other words, when styrene was used as a hydrogen acceptor, which preferentially adsorbs on the Pd nanoparticle surface in the presence of N-cyclohexylidene-anilines, various structurally diverse primary anilines were selectively synthesized from readily accessible NH3 and cyclohexanones. The Pd/HAP catalyst was reused several times though its catalytic performance gradually declined.
- Koizumi, Yu,Jin, Xiongjie,Yatabe, Takafumi,Miyazaki, Ray,Hasegawa, Jun-ya,Nozaki, Kyoko,Mizuno, Noritaka,Yamaguchi, Kazuya
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supporting information
p. 10893 - 10897
(2019/07/12)
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- Synthesis of Highly Enantioenriched Propelladienes and their Application as Ligands in Asymmetric Rh-Catalyzed 1,4-Additions
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The first synthesis of highly enantioenriched [4.3.3]propelladienes is reported. The novel bridged bicyclo[3.3.0] dienes were applied as steering ligands in the rhodium-catalyzed asymmetric arylation of cyclic enones. The catalytic system showed high catalytic activity, and the 1,4-adducts were obtained in good to excellent yields (46-99%) with enantioselectivities up to 96% ee.
- Pecchioli, Tommaso,Christmann, Mathias
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supporting information
p. 5256 - 5259
(2018/09/13)
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- Electronic and Steric Tuning of an Atropisomeric Disulfoxide Ligand Motif and Its Use in the Rh(I)-Catalyzed Addition Reactions of Boronic Acids to a Wide Range of Acceptors
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A novel chiral disulfoxide ligand pair bearing fluorine atoms at the 6 and 6′ position of its atropisomeric backbone, (M,S,S)- and (P,S,S)-p-Tol-6F-BIPHESO, was synthesized. Complexation to a rhodium(I) precursor gave rise to μ-Cl- and μ-OH-bridged rhodiu
- Zhao, Guang-Zhen,Foster, Daven,Sipos, Gellért,Gao, Pengchao,Skelton, Brian W.,Sobolev, Alexandre N.,Dorta, Reto
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p. 9741 - 9755
(2018/09/06)
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- A diastereomeric pair of sulfoxide-containing chiral MOP-type ligands: Preparation and application to rhodium-catalyzed asymmetric 1,4-addition reactions
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(R,SS)-Sulfoxide-MOP (L2) and (R,RS)-sulfoxide-MOP (L3) were developed as a diastereomeric pair of sulfoxide-containing chiral MOP-type ligands. These two ligands also represent the first monosulfoxide analogues of BINAP. The chiral ligand L2 was successfully applied to the highly enantioselective rhodium-catalyzed 1,4-addition between α,β-unsaturated ketones or esters and arylboronic acids, and exhibited a broad substrate scope when the reaction was performed using 1.5 mol% Rh in cyclohexane/H2O (10:1) at 40 °C under mild basic conditions.
- Hoshi, Takashi,Fujita, Masataka,Matsushima, Shouta,Hagiwara, Hisahiro,Suzuki, Toshio
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supporting information
p. 800 - 802
(2018/06/12)
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- Aqueous Asymmetric 1,4-Addition of Arylboronic Acids to Enones Catalyzed by an Amphiphilic Resin-Supported Chiral Diene Rhodium Complex under Batch and Continuous-Flow Conditions
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A rhodium-chiral diene complex immobilized on amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin (PS-PEG-diene?-Rh) has been developed. The immobilized rhodium-chiral diene complex (PS-PEG-diene?-Rh) efficiently catalyzed the asymmetric 1,4-addition of various arylboronic acids to cyclic or linear enones in water under batch conditions to give the corresponding β-arylated carbonyl compounds in excellent yields and with excellent enantioselectivity. The catalyst was readily recovered by simple filtration and reused 10 times without loss of its catalytic activity and enantioselectivity. Moreover, a continuous-flow asymmetric 1,4-addition in a flow reactor containing PS-PEG-diene?-Rh proceeded efficiently at 50 °C with retention of high enantioselectivity. Long-term continuous-flow asymmetric 1,4-addition during 12 h readily gave the desired product on a 10 g scale with high enantioselectivity.
- Shen, Guanshuo,Osako, Takao,Nagaosa, Makoto,Uozumi, Yasuhiro
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p. 7380 - 7387
(2018/07/29)
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- A novel, C2-symmetric, chiral bis-cyclosulfinamide-olefin tridentate ligand in Rh-catalyzed asymmetric 1,4-additions
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A C2-symmetric, chiral bis-cyclosulfinamide-olefin ligand composed of two 1-oxo-2,3-dihydro-1,2-benzisothiazole moieties with rigid skeletons and a conformationally flexible butenylene chain is disclosed for the first time. HRMS and 1/sup
- Zhang, Li,Tan, Mingchao,Zhou, Lihong,Zeng, Qingle
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supporting information
p. 2778 - 2783
(2018/06/11)
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- Synthesis of Cyclohexanones through a Catalytic Cationic Cyclization of Alkynols or Enynes
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A novel procedure for the synthesis of cyclohexanones from alkynol or enyne derivatives through a cationic cyclization has been developed. The key points to obtain the six-membered ring derivatives are the use of starting materials containing a terminal alkyne, the use of tetrafluoroboric acid as a promoter of the cationic cyclization, and the appropriate selection of 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) as solvent. This strategy can be extended to the biomimetic cationic cyclization of several terpene-derived polyenynes.
- Alonso, Pedro,Fontaneda, Raquel,Pardo, Pilar,Fa?anás, Francisco J.,Rodríguez, Félix
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supporting information
p. 1659 - 1662
(2018/03/23)
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- Palladium-catalyzed redox cascade for direct β-arylation of ketones
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Herein we report a full article about the detailed design and development of two palladium-catalyzed redox cascade methods that enable direct β-arylation of ketones. Palladium-catalyzed ketone dehydrogenation, aryl-X bond activation and conjugate addition were merged into a redox-neutral catalytic cycle. Non-metal-based aryl electrophiles were used as both the oxidant and the aryl source. The β-arylation with aryl iodides was achieved site-selectively with Pd(TFA)2/P(i-Pr)3 as the precatalyst and AgTFA as the iodide scavenger. Both cyclic and linear ketones can react to give β-aryl ketones with excellent functional group tolerance. The β-arylation with diaryliodonium salts was realized without stoichiometric heavy metal additives, and proved to be redox-neutral. A wider substrate scope regarding aryl groups and ketones was obtained for the arylation with diaryliodonium salts, and the possible involvement of palladium nanoparticles as the active catalyst was examined and discussed.
- Huang, Zhongxing,Dong, Guangbin
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p. 3253 - 3265
(2018/05/04)
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- Selective C(sp3)?H Aerobic Oxidation Enabled by Decatungstate Photocatalysis in Flow
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A mild and selective C(sp3)?H aerobic oxidation enabled by decatungstate photocatalysis has been developed. The reaction can be significantly improved in a microflow reactor enabling the safe use of oxygen and enhanced irradiation of the reaction mixture. Our method allows for the oxidation of both activated and unactivated C?H bonds (30 examples). The ability to selectively oxidize natural scaffolds, such as (?)-ambroxide, pregnenolone acetate, (+)-sclareolide, and artemisinin, exemplifies the utility of this new method.
- Laudadio, Gabriele,Govaerts, Sebastian,Wang, Ying,Ravelli, Davide,Koolman, Hannes F.,Fagnoni, Maurizio,Djuric, Stevan W.,No?l, Timothy
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supporting information
p. 4078 - 4082
(2018/03/21)
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- Synthesis, Structures, and Catalytic Properties of Dinuclear Iridium(I) Complexes with a Hexadentate Macrocyclic Diamine-Tetracarbene Ligand
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Two dinuclear macrocyclic IrI NHC complexes, [Ir2(L1)(COD)2](PF6)2 (1, COD = 1,5-cyclooctadiene) and [Ir2Cl(L1)(COD)]Cl (2), were prepared by the reaction between [{Ir
- Fei, Fan,Lu, Taotao,Yang, Chu-Fan,Chen, Xue-Tai,Xue, Zi-Ling
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p. 1595 - 1602
(2018/04/24)
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- Palladium-Catalyzed Direct β-C?H Arylation of Ketones with Arylboronic Acids in Water
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A palladium-catalyzed direct β-C?H arylation of ketones was developed under mild conditions in water, featuring commercially available arylboronic acids as nucleophilic aryl sources and o-iodoxybenzoic acid as the oxidant. The method provides a concise route to access β-arylated ketones. Preliminary studies indicated that direct asymmetric β-C?H arylation of ketones could be achieved by this strategy. (Figure presented.).
- Hu, Xiaoyun,Yang, Xiaobo,Dai, Xi-Jie,Li, Chao-Jun
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supporting information
p. 2402 - 2406
(2017/07/22)
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- Center chirality-axial chirality electron deficiency diphosphine ligand as well as synthesis and application thereof
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The invention discloses a center chirality-axial chirality electron deficiency diphosphine ligand as well as synthesis and application thereof. The electron deficiency diphosphine ligand is designed and synthesized by the following steps: by basing bis(di
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Paragraph 0037-0039
(2017/07/20)
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- Design and synthesis of chiral 1,10-phenanthroline ligand, and application in palladium catalyzed asymmetric 1,4-addition reactions
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Pd-catalyzed asymmetric 1,4-addition of phenylboronic acid to α,β-unsaturated carbonyl compounds was developed using chiral 1,10-phenanthroline derivative as ligand. Good yields (up to 97%), and high enantioselectivities (up to 97% ee) were achieved.
- Tamura, Masafumi,Ogata, Hayato,Ishida, Yuu,Takahashi, Yasunori
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supporting information
p. 3808 - 3813
(2017/09/15)
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- Reducing Diastereomorphous Bis(phosphane oxide) Atropisomers to One Atropisomerically Pure Diphosphane: A New Ligand and a Novel Ligand-Preparation Design
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1,1′-Biphenyl-2,2′-diphosphanes with an achiral bridge spanning C-5 and C-5′ form atropisomers that are enantiomers. Accessing them in an atropisomerically pure form requires resolving a racemic mixture thereof or of a bis(phosphane oxide) precursor. 1,1′-Biphenyl-2,2′-diphosphanes with a homochiral bridge spanning C-5 and C-5′ form atropisomers that are diastereomers. We synthesized the first compound of this kind 1) atropselectively and 2) under thermodynamic control—seemingly a first-time exploit in diphosphane synthesis. The selectivity-inducing step was a high-temperature reduction of two non-interconverting bis(phosphane oxide) atropisomers (60:40 mixture). It furnished the desired diphosphane atropisomerically pure (and atropconvergently because the yield was 67 %). This diphosphane proved worthwhile in Tsuji–Trost allylations, the Hayashi addition of phenylboronic acid to cyclohexenone, and the asymmetric hydrogenation of methyl acetoacetate (up to 95 % yield and 95 % ee).
- Sartorius, Frank,Trebing, Marc,Brückner, Charlotte,Brückner, Reinhard
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supporting information
p. 17463 - 17468
(2017/11/27)
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- Novel MOP-type H8-binaphthyl monodentate phosphite ligands and their applications in transition metal-catalyzed asymmetric 1,4-conjugate additions and hydroformylations
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A new series of monodentate phosphites based on the rigid, axially chiral monoesterified H8-BINOL, which are easy to prepare from the readily accessible phosphorylating reagents (Sa)- or (Ra)-1,1′-binaphthyl-2,2′-diylchlorophosphite and (Sa)- or (Ra)-1,1′-H8-binaphthyl-2,2′-diylchlorophosphite, have been synthesized. All ligands were purified on a silica gel column under a nitrogen atmosphere with moderate yields, and were white solids and air-stable at room temperature. These ligands afforded good to excellent enantioselectivities in the Cu-catalyzed 1,4-conjugate addition of 2-cyclohexenone with nucleophiles Et2Zn (96% ee) and with Ph2Zn (65% ee), 2-cyclopentenone with Et2Zn (95% ee), 2-cycloheptenone with Et2Zn (76% ee), and 5,6-dihydro-2H-pyran-2-one with Et2Zn (90% ee). In the Rh-catalyzed asymmetric hydroformylation of styrene, these ligands showed a chemoselectivity of >99% in aldehydes, and a satisfactory branched over linear ratio (96/4). Moreover, the sense of the enantiodiscrimination of the products was mainly determined by the configuration of the BINOL-based or H8-BINOL-based phosphocycle.
- Tian, Mi,Pang, Zeng-bo,Li, Hai-feng,Wang, Lai-lai
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supporting information
p. 330 - 337
(2017/02/18)
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- Pd NPs-Loaded Homochiral Covalent Organic Framework for Heterogeneous Asymmetric Catalysis
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We herein report the fabrication of a palladium nanoparticles (Pd NPs) loaded homochiral covalent organic framework using S-(+)-2-methylpiperazine and cyanuric chloride (Pd@CCOF-MPC) (2) via a very facile chemical approach. The chiral COF support of 1 (CC
- Ma, Hui-Chao,Kan, Jing-Lan,Chen, Gong-Jun,Chen, Cheng-Xia,Dong, Yu-Bin
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p. 6518 - 6524
(2017/08/18)
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- Role of Regioisomeric Bicyclo[3.3.0]octa-2,5-diene Ligands in Rh Catalysis: Synthesis, Structural Analysis, Theoretical Study, and Application in Asymmetric 1,2- and 1,4-Additions
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In order to study the impact of regioisomeric diene ligands on the formation and catalytic activity of Rh complexes, a series of C2- and CS-symmetric 2,5-disubstituted bicyclo[3.3.0]octa-2,5-dienes C2-L and CS-L, respectively, were synthesized from Weiss diketone by simultaneous deprotonation/electrophilic trapping of both oxo functions, and the catalytic behavior was studied in the presence of [RhCl(C2H4)2]2. Complexes [RhCl(C2-L)]2 bearing C2-symmetric ligands catalyzed effectively the asymmetric arylation of N-tosylaldimines to (S)-diarylamines with yields and ee values up to 99%. In Hayashi-Miyaura reactions, however, the complexes showed poor catalytic activity. When complexes [RhCl(CS-L)]2 with CS-symmetric ligand or mixtures of [RhCl(C2-L)]2 and [RhCl(CS-L)]2 were employed in 1,2-additions, racemic addition products were observed, suggesting a C=C isomerization of the diene ligands. X-ray crystal structure analysis of both Rh complexes formed from the [RhCl(C2H4)2]2 precursor and ligands C2-L and CS-L revealed that only the C2-symmetric ligand C2-L coordinated to the Rh, whereas CS-L underwent a Rh-catalyzed C=C isomerization to rac-C2-L, which then gave the racemic [RhCl(rac-C2-L)]2 complex. DFT calculations of the relative stabilities of the Rh complexes and the proposed intermediates provided a mechanistic rationale via Rh-mediated hydride transfer.
- Mühlh?user, Tina,Savin, Alex,Frey, Wolfgang,Baro, Angelika,Schneider, Andreas J.,D?teberg, Heinz-Günter,Bauer, Florian,K?hn, Andreas,Laschat, Sabine
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p. 13468 - 13480
(2017/12/26)
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- Palladium complexes with chiral imidazole ligands as potential catalysts for asymmetric C[sbnd]C coupling reactions
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Two palladium complexes of the type [Pd(im)2Cl2] containing chiral imidazole ligands (im?=?1-bornyloxymethylene imidazole, 1-fenchyloxymethylyne imidazole) were synthesized and structurally characterized. The square planar structure of one of the complexes was confirmed by the X-ray analysis. The new palladium complexes were tested as catalysts in various C[sbnd]C bond forming reactions, namely Suzuki–Miyaura, carbonylative Suzuki–Miyaura, asymmetric Heck-type coupling reactions and asymmetric conjugate addition of phenylboronic acid to heterocyclic acceptors. In all the reactions the cross-coupling products were obtained with high yield and selectivity under mild conditions. In case of coupling of 2,3-dihydrofuran with phenylboronic acid ee value ca. 10 was observed.
- Zawartka, Wojciech,Gniewek, Andrzej,Trzeciak, Anna M.
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p. 595 - 599
(2016/11/30)
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- Grignard Reagents on a Tab: Direct Magnesium Insertion under Flow Conditions
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An on-demand preparation of organomagnesium reagents is presented using a new flow protocol. The risks associated with the activation of magnesium are circumvented by a new on-column initiation procedure. Required amounts of solutions with a precise titration were obtained. Telescoped flow or batch reactions allow access to a diverse set of functional groups.
- Huck, Lena,De La Hoz, Antonio,Díaz-Ortiz, Angel,Alcázar, Jesus
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supporting information
p. 3747 - 3750
(2017/07/26)
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- Electronically deficient (Rax,S,S)-F12-C3-TunePhos and its applications in asymmetric 1,4-addition reactions
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A novel electronically deficient chiral diphosphine ligand (Rax,S,S)-F12-C3-TunePhos has been concisely synthesized. The electron-poor ligand features both chiral centers and chiral axis bearing fluoro-functional groups on
- Hu, Shu-Bo,Chen, Zhang-Pei,Zhou, Ji,Zhou, Yong-Gui
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supporting information
p. 1925 - 1929
(2016/04/19)
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