- 2,3-Wittig rearrangement by partial reduction of diallyl acetals with SmI2 in acetonitrile
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Diallyl acetals undergo reductive cleavage of an allyloxy group by SmI2 to generate α-allyloxy carbanions, which are transformed into homoallyl alcohols by 2,3-Wittig rearrangement.
- Hioki, Kazuhito,Kono, Kazuhiro,Tani, Shohei,Kunishima, Munetaka
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Read Online
- Visible Light-Promoted Recyclable Carbon Nitride-Catalyzed Dioxygenation of β,γ-Unsaturated Oximes
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A visible-light-induced dioxygenation of β,γ-unsaturated oximes for the synthesis of diverse useful isoxazolines bearing a hydroxyl moiety was developed by employing graphitic carbon nitride (g-C3N4) as a heterogeneous photocatalyst under an air atmosphere. Noted that, the eminent advantages of this metal-free protocol include step economy, easy operation, a recyclable photocatalyst, external reductant-/oxidant-free and mild reaction conditions. Additionally, mechanistic studies indicated hydroxyl radical was generated under the photocatalysis of g-C3N4.
- Fu, Xiao-Yang,Si, Ya-Feng,Qiao, Li-Peng,Zhao, Yu-Fen,Chen, Xiao-Lan,Yu, Bing
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supporting information
p. 574 - 580
(2021/11/13)
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- Organocatalytic Asymmetric Synthesis of Cyclic Acetals with Spirooxindole Skeleton
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An organocatalytic asymmetric synthesis of cyclic acetal with spirooxindole skeleton has been developed via a domino reaction between isatin and γ-hydroxy enones. Bifunctional squaramide catalyst with adamantyl motif was found to be the most effective for the cascade reaction. With 10 mol% of the catalyst, the desired products were obtained in 1.8:1 to 9:1 diastereo- and 86% to >99% enantioselectivities from a range of substituted isatins and γ-hydroxy enones. (Figure presented.).
- Shikari, Amit,Mandal, Koushik,Chopra, Deepak,Pan, Subhas Chandra
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supporting information
p. 58 - 63
(2021/11/09)
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- Nickel-Catalyzed Reductive Allylation of Aldehydes with Allyl Acetates
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Carbonyl allylation reactions constitute an important step in the formation of carbon-carbon reactions, and involve various related reactions that chiefly use allylmetal reagents. This report presents a nickel-catalyzed carbonyl allylation reaction using allyl acetate, which produces homoallyl alcohols in moderate to good yields, as an efficient methodology under reductive coupling conditions.
- Suzuki, Hiroyuki,Yamaguchi,Itoh, Akichika
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p. 1489 - 1494
(2020/12/13)
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- Photocatalytic Umpolung Synthesis of Nucleophilic π-Allylcobalt Complexes for Allylation of Aldehydes
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The concept of "umpolung"reactivity of π-allylmetal complexes has been developed as a powerful method for the allylation of aldehydes. This paper describes the photocatalytic umpolung strategy for the synthesis of nucleophilic allylcobalt complexes through a single-electron-transfer (SET) process. This strategy enables the metallaphotoredox allylation of carbonyls with allyl acetate using organic N,N-diisopropylethylamine as the terminal reductant bypassing the use of a stoichiometric amount of metals. Ultraviolet-visible spectroscopy was used to monitor the redox changes of cobalt in the reaction.
- Shi, Caizhe,Li, Fusheng,Chen, Yuqing,Lin, Shuangjie,Hao, Erjun,Guo, Zhuowen,Wosqa, Urwa Tul,Zhang, Dandan,Shi, Lei
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p. 2992 - 2998
(2021/03/09)
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- Copper-catalyzed radical oxyallylation of olefins for the construction of alkene-containing isoxazolines
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A radical-mediated approach to alkene oxyallylation using allylic oximes is described. The reaction proceeds under copper-catalytic redox-neutral conditions and tolerates various functional groups. This protocol thus enables the synthesis of structurally valuable isoxazolines and the introduction of a versatile olefin motif in a single step.
- He, Xiaoxue,Qian, Lijie,Dai, Yuyu,Yan, Xinhuan,Li, Xiaoqing,Xu, Xiangsheng
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supporting information
(2021/05/31)
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- Ni-Catalyzed 1,2-Diarylation of Alkenyl Ketones: A Comparative Study of Carbonyl-Directed Reaction Systems
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A nickel-catalyzed 1,2-diarylation of alkenyl ketones with aryl iodides and arylboronic esters is reported. Ketones with a variety of substituents serve as effective directing groups, offering high levels of regiocontrol. A representative product is diversified into a wide range of useful products that are not readily accessible via existing 1,2-diarylation reactions. Preliminary mechanistic studies shed light on the binding mode of the substrate, and Hammett analysis reveals the effect of electronic factors on initial rates.
- Apolinar, Omar,Derosa, Joseph,Engle, Keary M.,Karunananda, Malkanthi K.,Kleinmans, Roman,Li, Zi-Qi,Tran, Van T.,Wisniewski, Steven R.
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supporting information
p. 5311 - 5316
(2021/07/26)
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- Application of metallocene rare earth metal complex in catalyzing aldehyde and allyl boric acid reaction
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The invention discloses a preparation method of allyl alcohol. The preparation method comprises the following steps of: in an anhydrous anaerobic environment and an inert gas atmosphere, adding a tricyclopentadienyl rare earth metal complex into a reaction flask; adding n-heptaldehyde, performing uniform mixing; and adding allylboronic acid, and carrying out a reaction to prepare allyl alcohol. The method has the advantages of mild reaction conditions, improvement of the catalytic activity, reduction of the preparation difficulty of a catalyst, and reduction of post-treatment cost.
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Paragraph 0016; 0039-0040
(2020/10/19)
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- Recyclable Polyisobutylene-Bound HMPA as an Organocatalyst in Recyclable Poly(α-olefin) Solvents
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This work describes the synthesis of a PIB-bound hexamethylphosphoramide (HMPA) analog and its applications as a recyclable catalyst in allylation of aldehydes and reduction of enones in a recyclable poly(α-olefin) (PAO) polymeric solvent. Kinetic studies of the allylation reaction show that this PIB-bound HMPA analog is as active as HMPA in dichloromethane and PAO and that this PIB-bound catalyst is comparably reactive in heptane and in a PAO solvent. The PIB-bound HMPA catalyst has high phase selective solubility in PAO versus a polar solvent. By using this catalyst in a nonvolatile separable PAO solvent, this catalyst recyclability can be coupled to solvent recyclability, something that is less feasible in a conventional heptane solvent. The result is good recycling of catalyst and solvent through at least 5 cycles using simple gravity-based liquid/liquid extractions. This is in contrast to HMPA or conventional solvents which are less recyclable.
- Fu, Ying-Hua,Bergbreiter, David E.
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p. 6050 - 6058
(2020/10/19)
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- Enantioselective Synthesis of Isoxazolines Enabled by Palladium-Catalyzed Carboetherification of Alkenyl Oximes
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Reported here is a highly efficient Pd/Xiang-Phos catalyzed enantioselective carboetherification of alkenyl oximes with either aryl or alkenyl halides, delivering various chiral 3,5-disubstituted and 3,5,5-trisubstituted isoxazolines in good yields with u
- Chen, Mingjie,Li, Wenbo,Wang, Lei,Wang, Yuzhuo,Zhang, Junliang,Zhang, Kenan
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supporting information
p. 4421 - 4427
(2020/02/11)
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- Regioselective Synthesis of Arylsulfonyl Benzophenones via Aerobic Oxidative [3+3] Benzannulation Reactions
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Regioselective synthesis of 3-arylsulfonyl benzophenone derivatives via base mediated, aerial-oxidative [3+3] benzannulation of α,β-unsaturated aldehydes and 4-sulfonyl butenones is reported. A variety of readily available acyclic building blocks are tran
- Yadav, Deepak,Joshi, Prabhakar R.,Sharma, Sunil K.,Menon, Rajeev S.
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p. 6370 - 6374
(2020/10/19)
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- A Mechanochemical Zinc-Mediated Barbier-Type Allylation Reaction under Ball-Milling Conditions
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A ball-milling-enabled zinc-mediated Barbier-type allylation reaction is reported. Notably, running the reaction in this manner renders it effective irrespective of the initial morphology of the zinc metal. The process is operationally simple, does not re
- Yin, JieXiang,Stark, Roderick T.,Fallis, Ian A.,Browne, Duncan L.
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p. 2347 - 2354
(2020/02/04)
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- Picolinate-Directed Arene meta-C-H Amination via FeCl3 Catalysis
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Direct C-H functionalization of aromatic compounds is a powerful tool for organic synthesis; however, differentiation among the ubiquitous and often chemically similar C-H bonds remains a significant challenge. Conflation with coordinating or directing groups incorporated into the intended substrate has helped address these limitations, although access to remote sites remains limited. Herein, we report an operationally simple and sustainable direct meta-selective H2N amination of benzylic and related aromatic picolinates under conditions mild enough to modify polyfunctional and late-stage molecules.
- Anugu, Raghunath Reddy,Falck, John R.,Munnuri, Sailu
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supporting information
p. 5266 - 5271
(2020/04/08)
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- Electrochemical Chalcogenation of β,γ-Unsaturated Amides and Oximes to Corresponding Oxazolines and Isoxazolines
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The current report represents a transition-metal-free synthesis of oxazoline and isoxazoline derivatives by a tandem electro-oxidative chalcogenation-cyclization process. Both C?Se and C?S bond-forming protocols were developed without using any external oxidant and the reaction was performed at room temperature, open to the air. Using this methodology, 29 substituted oxazoline and 16 substituted isoxazoline derivatives were synthesized with up to 91% isolated yield. (Figure presented.).
- Baidya, Mrinmay,De Sarkar, Suman,Mahanty, Kingshuk,Maiti, Debabrata,Mallick, Samrat
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supporting information
(2020/02/04)
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- Nickel-Catalyzed Hydroarylation of in Situ Generated 1,3-Dienes with Arylboronic Acids Using a Secondary Homoallyl Carbonate as a Surrogate for the 1,3-Diene and Hydride Source
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The nickel-catalyzed hydroarylation of 1,3-dienes with arylboronic acids using a secondary homoallyl carbonate as a surrogate for the 1,3-diene and hydride source has been developed. The synthetic strategy allowed an efficient access to a wide array of hydroarylation products in high yields with high functional group compatibility without the use of an external hydride source. Mechanistic experiments indicated that the alkene-directed oxidative addition and subsequent β-hydride elimination would be a critical process in this transformation.
- Hamaguchi, Takashi,Kawatsura, Motoi,Takahashi, Yoshiyuki,Tsuji, Hiroaki
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supporting information
(2020/02/15)
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- Copper-catalyzed asymmetric cyanation of alkenes via carbonyl-assisted coupling of alkyl-substituted carbon-centered radicals
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Based on a copper-catalyzed radical relay strategy, the first copper-catalyzed asymmetric cyanation of alkyl-substituted alkenes has been developed. The reaction, featuring mild reaction conditions and excellent functional group compatibilities, provides
- Zhou, Song,Zhang, Guoyu,Fu, Liang,Chen, Pinhong,Li, Yibiao,Liu, Guosheng
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supporting information
p. 6299 - 6303
(2020/10/02)
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- Copper-Catalyzed Aerobic Cyclization of β,γ-Unsaturated Hydrazones with Concomitant CC Bond Cleavage
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A Cu-catalyzed aerobic oxidative cyclization of β,γ-unsaturated hydrazones for the preparation of pyrazole derivatives has been developed. The hydrazonyl radical promoted the cyclization, along with a concomitant CC bond cleavage of β,γ-unsaturated hydrazones. This process has been verified via several control experiments, including a radical-trapping study, an 18O-labeling method, and the identification of the possible byproducts. The advantages of this reaction include operational simplicity, a broad reaction scope, and a mild selective reaction process.
- Fan, Zhenwei,Feng, Jiahao,Hou, Yuchen,Rao, Min,Cheng, Jiajia
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supporting information
p. 7981 - 7985
(2020/11/02)
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- MnO2as a terminal oxidant in Wacker oxidation of homoallyl alcohols and terminal olefins
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Efficient and mild reaction conditions for Wacker-type oxidation of terminal olefins of less explored homoallyl alcohols to β-hydroxy-methyl ketones have been developed by using a Pd(ii) catalyst and MnO2 as a co-oxidant. The method involves mild reaction conditions and shows good functional group compatibility along with high regio- and chemoselectivity. While our earlier system of PdCl2/CrO3/HCl produced α,β-unsaturated ketones from homoallyl alcohols, the present method provided orthogonally the β-hydroxy-methyl ketones. No overoxidation or elimination of benzylic and/or β-hydroxy groups was observed. The method could be extended to the oxidation of simple terminal olefins as well, to methyl ketones, displaying its versatility. An application to the regioselective synthesis of gingerol is demonstrated.
- Fernandes, Rodney A.,Ramakrishna, Gujjula V.,Bethi, Venkati
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p. 6115 - 6125
(2020/10/27)
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- NHC Core Phosphonium Ylide-based Palladium(II) Pincer Complexes: The Second Ylide Extremity Makes the Difference
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The coordinating properties of N-heterocyclic carbene (NHC) (A), phenolate (B), and phosphonium ylide (C) moieties were investigated systematically through the preparation of a family of NHC, phosphonium ylide-based pincer ligands, where the third donor e
- Taakili, Rachid,Barthes, Cécile,Go?ffon, Amel,Lepetit, Christine,Duhayon, Carine,Valyaev, Dmitry A.,Canac, Yves
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p. 7082 - 7096
(2020/05/13)
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- Synthesis of Enantiomerically Pure 5,6-Dihydropyran-2-ones via Chemoenzymatic Sequential DKR-RCM Reaction
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The enantiomerically pure 5,6-dihydropyran-2-ones play a crucial role as the building blocks in the synthesis of various bioactive compounds. A new straightforward protocol toward enantiomerically pure 5,6-dihydropyran-2-ones based on enzymatic dynamic ki
- Koszelewski, Dominik,Borys, Filip,Brodzka, Anna,Ostaszewski, Ryszard
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supporting information
p. 1653 - 1658
(2019/01/24)
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- Nickel Catalyzed Intermolecular Carbonyl Addition of Aryl Halide
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In this study, we develop a nickel-catalyzed carbonyl arylation reaction employing aldehydes with aryl and allyl halides. Various aryl, α,β-unsaturated aldehyde and aliphatic aldehydes can be converted into their corresponding secondary alcohols in moderate-to-high yields. In addition, we extended this approach to develop an asymmetric reductive coupling reaction that combines nickel salts with chiral bisoxazoline ligands to give secondary alcohols with moderate enantioselectivity.
- Ishida, Seima,Suzuki, Hiroyuki,Uchida, Seiichiro,Yamaguchi, Eiji,Itoh, Akichika
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supporting information
p. 7483 - 7487
(2019/12/11)
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- Use of allylzinc halide as a source of halide: Differential addition of nucleophiles to Ts-aziridines and aldehydes under similar reaction conditions
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We have observed that the allylic zinc halide under identical reaction conditions acts in different modes for different electrophiles. For Ts-aziridines the halide part of the allylic halide has been introduced as a nucleophile and for the carbonyl compou
- Chatterjee, Rana,Samanta, Satyajit,Mukherjee, Anindita,Santra, Sougata,Zyryanov, Grigory V.,Majee, Adinath
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supporting information
p. 276 - 283
(2019/01/04)
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- Active bismuth mediated allylation of carbonyls/N-tosyl aldimines and propargylation of aldehydes in water
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Abstract: Active bismuth is synthesized by the chemical reduction of bismuth trichloride using freshly prepared sodium stannite solution as the reducing agent at room temperature. The as-synthesized active bismuth is applied as a reagent for the synthesis of homoallyl alcohol/homopropargyl alcohol from allyl bromide/propargyl bromide and carbonyl compounds in water at 50°C. The homoallyl amines are also synthesized from N-tosyl aldimines and allyl bromide using active bismuth reagent in good yields. No assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere is required for this reaction. The waste bismuth material obtained after the completion of the organic reaction can be reduced to active bismuth by sodium stannite solution and successfully reused for mediating the allylation of aldehydes. Graphical Abstract:: Synopsis Active bismuth mediated allylation/crotylation of aldehydes is developed in water to get homoallyl alcohols. The method is also applied for the allylation of N-tosyl aldimines and propargylation of aldehydes in water to achieve the homoallyl amines and homopropargyl alcohols, respectively. The reactions do not require the assistance of organic co-solvent, co-reagent, phase transfer catalyst or inert atmosphere.[Figure not available: see fulltext.].
- Sawkmie, Micky Lanster,Paul, Dipankar,Khatua, Snehadrinarayan,Chatterjee, Paresh Nath
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- Syntheses of 4-Acetoxy-or acetylthio-2-substituted tetrahydrothiophene
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The generality of a three-step route for the preparation of 4-Acetoxy-2-Alkyltetrahydrothiophenes was investigated, which started from 1-Alken-4-ols including epoxidation, mesylation and intramolecular nucleophilic substitution. 4-Acetoxy-2-Alkyltetrahydr
- Li, Yaxi,Ding, Rui,Liu, Yongguo,Ma, Bianbian,Sun, Baoguo,Tian, Hongyu
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p. 254 - 272
(2018/02/22)
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- Visible light-driven photocatalytic generation of sulfonamidyl radicals for alkene hydroamination of unsaturated sulfonamides
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A visible light-driven photocatalytic generation of sulfonamidyl radicals, and application to intramolecular alkene hydroamination, has been accomplished, providing a mild and efficient approach to various functionalized isoxazolidines. The success of this protocol is based on the strategy of oxidative deprotonation electron transfer by merging the base and the photocatalyst under visible light irradiation, obviating installation of a photolabile handle or stoichiometric external oxidants.
- Chen, Jun,Guo, Hong-Mei,Zhao, Quan-Qing,Chen, Jia-Rong,Xiao, Wen-Jing
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supporting information
p. 6780 - 6783
(2018/06/26)
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- Water-Compatible Synthesis of 2-Trifluoromethyl-1,3-Dioxanes
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A water-compatible method for the diastereoselective synthesis of 2-trifluormethyl-1,3-dioxanes is described. The reaction proceeds under mild reaction conditions using simple inorganic bases; it has a very good substrate scope and can be performed with different Michael acceptors. Additionally, the reaction products can be further functionalized, showing an excellent perspective for future applications.
- Becerra-Figueroa, Liliana,Tiniakos, Alexander F.,Prunet, Jo?lle,Gamba-Sánchez, Diego
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supporting information
p. 6929 - 6932
(2018/11/25)
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- Ruthenium-Catalyzed Direct Transformation of Alkenyl Oximes to 5-Cyanated Isoxazolines: A Cascade Approach Based on Non-Stabilized Radical Intermediate
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A ruthenium-catalyzed ammoxidation of alkenyl oximes under mild and neutural condtions is described. In this method, tert-butyl nitrite plays a dual role, acting as an oxidant as well as a nitrogen source. This reaction avoids using any toxic radical initiators or cyanide reagents. This convenient and practical method offers an easy access to 5-cyanated isoxazolines in good to high yields, and shows good functional group tolerance and high efficiency. It is rather remarkable that this new reaction provides a strategically distinct approach based on non-stabilized radical intermediate and constructs C–O and C≡N triple bonds in a single-step. Moreover, the difunctionalization of unactivated olefins bearing oximes has been realized.
- Wang, Dan-Jun,Chen, Bei-Yi,Wang, Yi-Qi,Zhang, Xiao-Wei
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supporting information
p. 1342 - 1346
(2018/04/02)
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- Copper-Promoted 6- endo-trig Cyclization of β,γ-Unsaturated Hydrazones for the Synthesis of 1,6-Dihydropyridazines
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A novel and efficient strategy for the synthesis of 1,6-dihydropyridazines via copper-promoted 6-endo-trig cyclization of readily available β,γ-unsaturated hydrazones have been developed. A series of 1,6-dihydropyridazines have been synthesized by this method with good yields, high functional group tolerance, and remarkable regioselectivity under mild conditions. Importantly, the 1,6-dihydropyridazines can be efficiently converted to biologically important pyridazines in the presence of NaOH.
- Guo, Yong-Qiang,Zhao, Mi-Na,Ren, Zhi-Hui,Guan, Zheng-Hui
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supporting information
p. 3337 - 3340
(2018/06/11)
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- An organoantimony complex with intramolecular N?→?Sb coordination as effective and recyclable catalyst for the allylation of aldehydes with tetraallyltin
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An air-stable hypervalent organoantimony (III) triflate complex (PhN(CH2C6H4)2SbOSO2CF3) having intramolecular N?→?Sb coordination was synthesized and characterized by techniques such as s
- Tan, Nianyuan,Nie, Tong,Au, Chak-Tong,Lan, Donghui,Wu, Shuisheng,Yi, Bing
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supporting information
p. 2592 - 2595
(2017/06/13)
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- Copper-mediated oxysulfonylation of alkenyl oximes with sodium sulfinates: a facile synthesis of isoxazolines featuring a sulfone substituent
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A novel and efficient Cu(OAc)2-mediated oxysulfonylation of alkenyl oximes with sodium sulfonates was developed. The reactions are easy to conduct, occur under mild conditions, and form a broad range of sulfone-substituted isoxazolines in good yields.
- Wang, Li-Jing,Chen, Manman,Qi, Lin,Xu, Zhidong,Li, Wei
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supporting information
p. 2056 - 2059
(2017/02/15)
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- Lewis Acid Catalyzed [3+3] Annulation of Donor–Acceptor Cyclopropanes with γ-Hydroxyenones: Access to Highly Functionalized Tetrahydropyrans
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Donor–acceptor cyclopropanes were engaged in a [3+3]-annulation reaction with γ-hydroxyenones. Sc(OTf)3was found to be the best catalyst, and 2,4,4,5-tetrasubstituted tetrahydropyran products were obtained in good yields under mild reaction con
- Mondal, Keshab,Pan, Subhas Chandra
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supporting information
p. 534 - 537
(2017/02/05)
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- Nucleo-Palladation-Triggering Alkene Functionalization: A Route to γ-Lactones
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An unprecedented strategy for the highly effective synthesis of γ-lactones from homoallylic alcohols was achieved by palladium catalysis in one step. The protocol affords aryl, alkyl, and spiro γ-lactones directly from readily available homoallylic alcohols in good yields with excellent functional group tolerance and high chemoselectivity under mild conditions.
- Zheng, Meifang,Chen, Pengquan,Huang, Liangbin,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 5756 - 5759
(2017/11/10)
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- Palladacycles having normal and spiro chelate rings designed from bi- and tridentate ligands with an indole core: Structure, synthesis and applications as catalysts
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1-Pyridin-2-ylmethyl-1H-indole-3-carbaldehyde and 1-((1-benzyl-1H-1,2,3-triazol-4-yl)methyl)-1H-indole-3-carbaldehyde were synthesized. Their condensation with benzyl amine resulted in indole core containing Schiff bases benzyl-(1-pyridin-2-ylmethyl-1H-in
- Singh, Mahabir P.,Saleem, Fariha,Pal, Ram S.,Singh, Ajai K.
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p. 11342 - 11352
(2017/10/05)
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- A ionic the bistriphenyl make PVC possess enough preparation and application of (V) complex
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The invention provides a preparation method of an ionic type bis-triphenyl organic antimony (V) complex and a method for synthesizing allyl alcohol compounds under catalysis of the ionic type bis-triphenyl organic antimony (V) complex. The complex is a cationic type organic antimony complex, wherein two antimony atoms in the complex are bridged by virtue of oxygen atoms and are pentavalent; and each antimony atom is in coordination with one water molecule, and an ionic bond is formed by the entire organic antimony cationic part with corresponding anions. The synthetic method comprises the following step: by taking the bis-triphenyl organic antimony (V) complex as a catalyst, taking a commonly-used organic solvent as a reaction solvent, and taking aldehyde and tetraallyltin as raw materials, performing reaction. The synthetic method can be used for providing a novel low-cost and 'green' route for preparing the allyl alcohol compounds, and has the advantages that target product selectivity and yield are high, the catalyst can be repeatedly used, corresponding ketone can be obtained by performing simple column chromatography separation on the product, and the whole reaction and separation process is simple to operate and is green and environment-friendly.
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Paragraph 0050; 0051
(2017/01/02)
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- A Mild, efficient protocol for the synthesis of homoallylic alcohols using potassium allyltrifluoroborate promoted by salicylic acid
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Background: In the current decade, organotrifluoroborates have attained remarkable development in Chemistry and Materials. This can be evidenced by the increasing number of articles, review articles and patents devoted to this subject. As a consequence, the number of citations derived from papers dealing with this subject has experienced an exponential growth in the last years. The aim of this paper to describe a methodology based on the use of potassium allyltrifluoroborate for the synthesis of homoallylic alcohols using water as a co-solvent and under mild reaction conditions. Methods: The methodology is very robust (wide range of aldehydes) and simple, it uses low catalyst loadings and it is synthetically useful because it could be applied for the synthesis of more complex compounds. In addition, detailed experimental procedures, including the preparation of the starting materials, as well as the corresponding 1H, 13C, 19F and 11B spectra for all synthesized compounds are provided. Results: The method is environmentally friendly while it uses water as a solvent and the desired compounds containing different functionalities were obtained in moderate to good yields (60-93%) without the need of further purification in a very chemo- and regioselective way. Conclusion: Salicylic acid can efficiently promote the allylation of aldehydes using potassium allyltrifluoroborate at room temperature to yield the corresponding homoallylic alcohols in moderate to good yields. The method is efficient and environmentally friendly while it uses water as co-solvent. In addition the method is regio- and chemoselective and could be applied in the synthesis of more complex homoallylic alcohols.
- Silva, Jadson F.,Lima, Josefa A.C.,De Freitas, Jucleiton J.R.,Freitas, Ladjane P.S.R.,Menezes, Paulo H.,Freitas, Juliano C.R.
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- Palladium(0)-mediated cyclization-coupling of β,γ-unsaturated oximes and aryl iodides
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The tandem palladium(0)-mediated nucleometalation-cross coupling of β,γ-unsaturated oximes with aryl iodides has been shown to provide the expected 3,5-disubstituted 2-isoxazolines in acceptable yields (11-78%). The addition of a weak base is required for product formation. Some influence on the yield of the reaction is noted in the electronic character of the aryl iodide used in the reaction. Exploration of the substitution patterns on the reactants has led to a proposed mechanism involving a palladium(II)-catalyzed nucleometalation/cyclization followed by reductive elimination of palladium(0) with concomitant coupling to an arene.
- Mikesell, Joshua,Mosher, Michael D.
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p. 1011 - 1013
(2016/02/16)
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- Ter-pyridine catalyzed allylation of aldehydes and ketones under metal-free condition
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Ter-pyridine derivatives were found to be potential catalyst for homoallylation of carbonyl groups. High yields of the products with short reaction times of ~2 h were observed in several cases. These new catalysts work efficiently with the simple reagent such as allyl magnesium bromide and hence can avoid the use of other sensitive or toxic reagents. It was found that the presence of polar groups on the catalysts made them extremely efficient without the presence of any metal salts.
- Datilus, Vicklyn,Abdulkarim, Mary,Patrizio, Andrew,Kaur, Parminder
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supporting information
p. 2778 - 2781
(2016/06/09)
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- Waste management in zinc promoted allylation of aldehyde
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By using an efficient, sustainable and green procedure, the waste zinc material in Zn(0) promoted Grignard-Barbier type allylation of aldehydes has been successfully utilized as a reusable material for the adsorption of various dyes and also converted int
- Pratihar, Sanjay,Kakoty, Anindita,Sarmah, Kasturi
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p. 5347 - 5356
(2016/07/06)
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- Mild bottom-up synthesis of indium(0) nanoparticles: Characterization and application in the allylation of carbonyl compounds
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Very reactive, monodisperse (4.0 ± 0.5 nm) spherical indium(0) nanoparticles have been generated in situ, in a simple, mild and efficient way, by fast reduction of commercially available indium(iii) chloride with lithium sand and a catalytic amount of 4,4′-di-tert-butylbiphenyl (DTBB) in THF, at room temperature, and in the absence of any anti-agglomeration additives or ligands. The as-synthesized bare InNPs were applied for the allylation of a variety of aldehydes and ketones. For most of the compounds tested, the corresponding homoallylic alcohols were obtained as the major product in good to excellent yield.
- Dorn, Viviana,Chopa, Alicia,Radivoy, Gabriel
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p. 23798 - 23803
(2016/03/12)
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- Organocatalytic Redox Isomerization of Electron-Deficient Allylic Alcohols: Synthesis of 1,4-Ketoaldehydes
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An organocatalytic redox isomerization strategy has been developed for the synthesis of 1,4-ketoaldehydes. DABCO was found to be the best catalyst for the isomerization of -hydroxy enones. With 20 mol % of DABCO as catalyst and DMSO as the solvent high yi
- Mondal, Keshab,Mondal, Buddhadeb,Pan, Subhas Chandra
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p. 4835 - 4840
(2016/07/06)
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- Metal-Free Autoxidative Nitrooxylation of Alkenyl Oximes with Molecular Oxygen
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A metal-free aerobic autoxidative nitrooxylation of alkenyl oximes mediated by tert-butyl nitrite is described. Molecular oxygen is used as the oxidizing reagent, avoiding use of organic trapping reagents such as 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMP
- Zhang, Xiao-Wei,Xiao, Zu-Feng,Zhuang, Yan-Jun,Wang, Mei-Mei,Kang, Yan-Biao
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supporting information
p. 1942 - 1945
(2016/07/06)
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- Transition-metal-free oxychlorination of alkenyl oximes:: In situ generated radicals with tert -butyl nitrite
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Oxychlorination of alkenyl oximes is harder compared to the analogous oxybromination or oxyiodination because of the difficulty associated with the formation of chlorine cations or radicals. A transition-metal-free oxychlorination of alkenyl oximes has be
- Zhang, Xiao-Wei,Xiao, Zu-Feng,Wang, Mei-Mei,Zhuang, Yan-Jun,Kang, Yan-Biao
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supporting information
p. 7275 - 7281
(2016/08/05)
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- Palladacycles of unsymmetrical (N,C-,E) (E = S/Se) pincers based on indole: Their synthesis, structure and application in the catalysis of Heck coupling and allylation of aldehydes
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Unsymmetrical (N,C,E)-type pincer ligand precursors [L1 and L2: E = S/Se] with an indole core were synthesized for the first time by the condensation of 1-(2-phenylsulfanyl/selenylethyl)-1H-indole-3-carbaldehyde with benzyl amine. The synthetic protocols
- Singh, Mahabir P.,Saleem, Fariha,Rao, Gyandshwar K.,Kumar,Joshi, Hemant,Singh, Ajai K.
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p. 6718 - 6725
(2016/05/09)
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- Strong Lewis acids of air-stable binuclear triphenylantimony(V) complexes and their catalytic application in C-C bond-forming reactions
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Two air-stable novel Lewis acids of triphenylantimony(V) pentafluorbezenesulfonates (2) and perfluorooctanesulfonates (3) were successfully synthesized and characterized. X-ray studies and thermo-gravimetric analysis found that these complexes showed high anti-hydrolyzability and thermal stability. The high catalytic activity and excellent recyclability of these complexes were achieved in the Michael addition reaction and the allylation reaction. On account of their stability, storability, as well as catalytic efficiency, these complexes should find a broad range of utility in organic synthesis.
- Li, Ningbo,Qiu, Renhua,Zhang, Xiaohong,Chen, Yun,Yin, Shuang-Feng,Xu, Xinhua
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p. 4275 - 4281
(2015/06/08)
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- Oxime-mediated oxychlorination and oxybromination of unactivated olefins
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An oxime-mediated oxychlorination and oxybromination of unactivated olefins relying on palladium catalysis has been developed. A wide range of chlorinated and brominated isoxazolines has been synthesized in moderate to good yields. To demonstrate the value of the method, the brominated isoxazoline has been further converted to other useful synthetic feedstock.
- Dong, Kui-Yong,Qin, Hai-Tao,Liu, Feng,Zhu, Chen
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supporting information
p. 1419 - 1422
(2015/03/04)
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- CuI catalyzed Barbier type allylation of aldehyde in presence of S1,S2-dipyridin-2-yl ferrocene-1,1′-dicarbothioate as ligand
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Ferrocene based ligand S1 ,S2-dipyridin-2-yl ferrocene-1,1′-dicarbothioate has been prepared from 1,1′-ferrocene-dicarboxylic acid. The ligand has been used successfully in the SnCl2.2H2O mediated Barbier type a
- Kashyap, Bishwapran,Phukan, Prodeep
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p. 662 - 670
(2015/05/27)
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- Synthesis of active tin: An efficient reagent for allylation reaction of carbonyl compounds
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High purity Sn(0) has been obtained as a result of reduction of SnO by sodium stannite (Na2SnO2) in aqueous solution. The process stands unique for the production of tin metal. The as-synthesized tin finds applications in synthetic organic chemistry as a reagent for the allylation of aldehydes and ketones in distilled water at room temperature to give rise to the corresponding homoallylic alcohols with high yield. The reaction occurs without the assistance of heat, ultrasonic vibration, co-solvents/co-reagents, etc. Enhancement of the reaction rate of allylation was observed in water rather than THF. The manipulation of allylation reaction becomes easy with active tin material.
- Sinha, Arun Kumar,Sil, Amit,Sasmal, Anup Kumar,Pradhan, Mukul,Pal, Tarasankar
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p. 1685 - 1690
(2015/03/30)
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- Iodine(III)-Mediated Oxy-fluorination of Alkenyl Oximes: An Easy Path to Monofluoromethyl-Substituted Isoxazolines
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A highly regioselective intramolecular oxy-fluorination of alkenyl oximes was achieved. This new transformation represents an efficient method for the preparation of monofluoromethyl-substituted isoxazolines. The synthetic application of the oxy-fluorinat
- Kong, Weidong,Guo, Quanping,Xu, Zhaoqing,Wang, Guoqiang,Jiang, Xianxing,Wang, Rui
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supporting information
p. 3686 - 3689
(2015/08/18)
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- Efficient synthesis of homoallylic alcohols/amines from allyltributylstannane and carbonyl compounds/imines using iodine as catalyst under acetic acid-water medium
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This paper describes a general method for the synthesis of homoallylic alcohols and amines by nucleophilic addition reaction of allyltributylstannane to carbonyl compounds and aldimines where iodine acts as a catalyst in H2O/acetic acid (1:1) medium. Only 10 mol% of I2 is required for various organic transformations. By using this process, various homoallylic alcohols and amines are produced in good to excellent yields.
- Kalita, Pabitra Kumar,Borthakur, Susanta Kumar,Das, Runumi,Choudhury, Chandan Jyoti
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supporting information
p. 2444 - 2453
(2015/11/10)
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- Strong Lewis acid air-stable cationic titanocene perfluoroalkyl(aryl) sulfonate complexes as highly efficient and recyclable catalysts for C-C bond forming reactions
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A series of strong Lewis acid air-stable titanocene perfluoroalkyl(aryl) sulfonate complexes Cp2Ti(OH2)2(OSO 2X)2·THF (X = C8F17, 1·THF; X = C4F9, 2·H2O· THF; X = C6F5, 3) were successfully synthesized by the treatment of Cp2TiCl2 with C8F 17SO3Ag, C4F9SO3Ag and C6F5SO3Ag, respectively. In contrast to well-known titanocene bis(triflate), these complexes showed no change in open air over three months. TG-DSC analysis showed that 1·THF, 2·H 2O·THF and 3 were thermally stable at 230 °C, 220°C and 280°C, respectively. Conductivity measurements showed that these complexes underwent ionic dissociation in CH3CN solution. X-ray analysis results confirmed that 2·H2O·THF and 3 were cationic. ESR spectra showed that the Lewis acidity of 1·THF (1.06 eV) was higher than that of Sc3+ (1.00 eV) and Y3+ (0.85 eV). UV/Vis spectra showed a significant red shift due to the strong complex formation between 10-methylacridone and 2·H2O·THF. Fluorescence spectra showed that the Lewis acidity of 2 (λem = 477 nm) was higher than that of Sc3+ (λem = 474 nm). These complexes showed high catalytic ability in various carbon-carbon bond forming reactions. Moreover, they show good reusability. Compared with 1·THF, 2·H2O·THF and 3 exhibit higher solubility and better catalytic activity, and will find broad applications in organic synthesis. This journal is the Partner Organisations 2014.
- Li, Ningbo,Wang, Jinying,Zhang, Xiaohong,Qiu, Renhua,Wang, Xie,Chen, Jinyang,Yin, Shuang-Feng,Xu, Xinhua
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supporting information
p. 11696 - 11708
(2014/07/22)
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- Catalytic organic reactions on the surface of silver(I) oxide in water
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We have developed Ag2O-catalyzed allylation reactions of aldehydes with allylsilanes in water, providing homoallylic alcohols in high yields with high anti-selectivities. It was found that the reactions proceeded not in the water solution but o
- Ueno, Masaharu,Tanoue, Arata,Kobayashi, Shu
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supporting information
p. 1867 - 1869
(2015/01/09)
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