- Rhodium-Catalyzed Regioselective Hydroformylation of Alkynes to α,β-Unsaturated Aldehydes Using Formic Acid
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A rhodium-catalyzed hydroformylation of alkynes with formic acid was developed. The method provides α,β-unsaturated aldehydes in high yield and E-selectivity without the need to handle toxic CO gas.
- Fan, Chao,Hou, Jing,Chen, Yu-Jia,Ding, Kui-Ling,Zhou, Qi-Lin
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supporting information
p. 2074 - 2077
(2021/04/05)
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- Palladium-Catalyzed Cascade Dearomative Spirocyclization and C?H Annulation of Aromatic Halides with Alkynes
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Described herein is a palladium-catalyzed intermolecular dearomative annulation of aryl halides with alkynes, which provides a rapid approach to a class of structurally unique spiroembedded polycyclic aromatic compounds. The cascade process is accomplished by a sequential alkyne migratory insertion, Heck-type dearomatization, and C-H bond annulation. Further optoelectronic study indicated this fused spirocyclic scaffold could be a potential host material for OLEDs, as exemplified by a fabricated red PhOLED device with a maximum external quantum efficiency of 23.0%.
- Liao, Xingrong,Zhou, Fulin,Bin, Zhengyang,Yang, Yudong,You, Jingsong
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supporting information
p. 5203 - 5207
(2021/07/19)
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- Synthesis of Diarylethynes from Aryldiazonium Salts by Using Calcium Carbide as an Alkyne Source in a Deep Eutectic Solvent
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An efficient method for the synthesis of diarylethynes from aryldiazonium salts by using calcium carbide as an alkyne source at room temperature in a deep eutectic solvent is described. The salient features of this protocol are an inexpensive and easy-to-handle alkyne source, a nonvolatile and recyclable solvent, mild conditions, and a simple workup procedure.
- Ma, Xiaolong,Li, Zheng
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supporting information
p. 631 - 635
(2020/12/28)
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- Synthesis of Bidentate Nitrogen Ligands by Rh-Catalyzed C-H Annulation and Their Application to Pd-Catalyzed Aerobic C-H Alkenylation
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A new class of bidentate ligands was prepared by a modular approach involving Rh-catalyzed C-H annulation reactions. The resulting conformationally constrained ligands enabled the Pd-catalyzed C-H alkenylation at electron-rich and sterically less hindered positions of electron-rich arenes while promoting the facile oxidation of Pd(0) intermediates by oxygen. This newly introduced ligand class is complementary to the ligands developed for Pd-catalyzed oxidative reactions and may find broad application in transition-metal-catalyzed reactions.
- Kim, Hyun Tae,Kang, Eunsu,Kim, Minkyu,Joo, Jung Min
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supporting information
p. 3657 - 3662
(2021/05/10)
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- Rh(iii)-Catalyzed three-component cascade annulation to produce theN-oxopropyl chain of isoquinolone derivatives
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Developing powerful methods to introduce versatile functional groups at theN-substituents of isoquinolone scaffolds is still a great challenge. Herein, we report a novel three-component cascade annulation reaction to efficiently construct theN-oxopropyl chain of isoquinolone derivativesviarhodium(iii)-catalyzed C-H activation/cyclization/nucleophilic attack, with oxazoles used both as the directing group and potential functionalized reagents.
- He, Yuan,Liao, Xian-Zhang,Dong, Lin,Chen, Fen-Er
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supporting information
p. 561 - 567
(2021/02/06)
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- The ruthenium(ii)-catalyzed C-H olefination of indoles with alkynes: The facile construction of tetrasubstituted alkenes under aqueous conditions
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An environmentally-friendly and facile protocol for the construction of tetrasubstituted alkenes has been established with Ru(ii)-catalyzed C-H bond functionalizations under mild conditions. The method features the usage of readily available substrates, without external oxidants and additives, 100% atom economy, and excellent regioselectivity, thus enhancing the practicability of this protocol. Moreover, this transformation proceeded smoothly under aqueous conditions and could be extended to the gram scale. N-Methoxyamide, as a directing group (DG), played a vital role in the transformation.
- Li, Ming,Yao, Tian-Yu,Sun, Sheng-Zheng,Yan, Ting-Xun,Wen, Li-Rong,Zhang, Lin-Bao
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supporting information
p. 3158 - 3163
(2020/05/08)
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- Rhodium-Catalyzed Spiro Indenyl Benzoxazine Synthesis via C-H Activation/Annulation of 3-Aryl-2H-Benzo[b][1,4]oxazines and Alkynes
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The rhodium (III)-catalyzed annulation of 3-Aryl-2H-Benzo[b][1,4]oxazines with alkynes via C–H activation has been developed. This reaction afforded a series of spiro indenyl benzoxazine in high yields under mild reaction condition with good functional group tolerance.
- Tan, Heng,Laishram, Ronibala Devi,Zhang, Xuexin,Shi, Guangrui,Li, Kangkui,Chen, Jingchao
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supporting information
p. 4542 - 4546
(2020/07/04)
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- Photo-induced and Rapid Labeling of Tetrazine-Bearing Proteins via Cyclopropenone-Caged Bicyclononynes
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Inverse electron-demand Diels–Alder cycloadditions (iEDDAC) between tetrazines and strained alkenes/alkynes have emerged as essential tools for studying and manipulating biomolecules. A light-triggered version of iEDDAC (photo-iEDDAC) is presented that confers spatio-temporal control to bioorthogonal labeling in vitro and in cellulo. A cyclopropenone-caged dibenzoannulated bicyclo[6.1.0]nonyne probe (photo-DMBO) was designed that is unreactive towards tetrazines before light-activation, but engages in iEDDAC after irradiation at 365 nm. Aminoacyl tRNA synthetase/tRNA pairs were discovered for efficient site-specific incorporation of tetrazine-containing amino acids into proteins in living cells. In situ light activation of photo-DMBO conjugates allows labeling of tetrazine-modified proteins in living E. coli. This allows proteins in living cells to be modified in a spatio-temporally controlled manner and may be extended to photo-induced and site-specific protein labeling in animals.
- Mayer, Susanne V.,Murnauer, Anton,von Wrisberg, Marie-Kristin,Jokisch, Marie-Lena,Lang, Kathrin
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supporting information
p. 15876 - 15882
(2019/10/28)
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- Production method of diaryl alkyne compound
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The invention discloses a production method of a diaryl alkyne compound. The production method of the diaryl alkyne compound comprises the steps of under protection of nitrogen, placing a bromobenzenesubstrate, alkynol, a palladium catalyst, an organic phosphine ligand and inorganic alkali into a reaction container, then adding a solvent, heating the reaction container for reaction, after the reaction container is cooled to room temperature, adding a saturated ammonium chloride solution for quenching, and then conducting extraction and column chromatography isolation and purification to obtain the diaryl alkyne compound. According to the production method of the diaryl alkyne compound, the aryl bromide and the alkynol which are simple and easy to obtain are used as raw materials, and through the palladium-catalyzed coupling reaction, the diaryl alkyne compound is obtained. The reaction raw materials are simple and easy to obtain, reaction conditions are mild, several defects in a traditional synthesis method are overcome, for example, the defect that when calcium carbide is used as a raw material, the release speed of acetylene cannot be controlled is overcome, the defect that when terminal alkyne is used as a raw material, a product and the raw material are hard to separate due to similar polarity is overcome, and the like. The method also has good performance in amplification reaction, so that the method has great application prospects.
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Paragraph 0074-0075; 0081
(2019/10/01)
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- Palladium-catalyzed sequential three-component reactions to access vinylsilanes
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A palladium-catalyzed sequential three-component reaction has been developed. The palladacycles, generated through cascade reactions of aryl halides and alkynes, are the key intermediates and react with hexamethyldisilane to form disilylated products. The reaction represents a useful preparative method for vinylsilanes, and the vinylsilanes can be transformed into tetrasubstituted alkenes.
- Zhou, Bo,Lu, Ailan,Shao, Changdong,Liang, Xinda,Zhang, Yanghui
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p. 10598 - 10601
(2018/09/25)
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- The Synthesis of Benzofulvenes through Palladium-Catalyzed Sequential Three-Component Reactions
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An approach for the synthesis of benzofulvenes has been developed through palladium-catalyzed sequential three-component reactions. The reactions likely involve C,C-palladacycles as the key intermediates. The palladacycles are generated through cascade reactions of aryl halides and alkynes, and then reacted with CH2Br2 to form benzofulvenes as the final products. (Figure presented.).
- Zhou, Bo,Wu, Zhuo,Qi, Weixin,Sun, Xueliang,Zhang, Yanghui
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supporting information
p. 4480 - 4484
(2018/10/31)
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- Synthesis of Indoles through Palladium-Catalyzed Three-Component Reaction of Aryl Iodides, Alkynes, and Diaziridinone
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The three-component reaction of aryl iodides, alkynes, and diaziridinone is described. The reaction provides an innovative synthetic approach for indoles. The approach features high efficiency, broad substrate scope, and excellent regioselectivity. C,C-Pa
- Zhou, Bo,Wu, Zhuo,Ma, Ding,Ji, Xiaoming,Zhang, Yanghui
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supporting information
p. 6440 - 6443
(2018/10/20)
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- Preparation method of diaryl acetylene compounds
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The invention relates to preparation of an organic compound, and aims to provide a preparation method of diaryl acetylene compounds. The preparation method includes steps of adding associated tribromomethylarene compound and copper in a reactor to perform deoxidizing treatment; dissolving polyamine in a proper amount of anhydrous and oxygen-free solvent, and then adding to the reactor; performingcoupling reaction at 30-80DEG C for 3-12 hours; separating and purifying to obtain diaryl acetylene compounds. The preparation is gentle in synthesis condition and the reaction has good compatibilityto different functional groups; the raw material associated tribromomethylarene compound is convenient to compound and has different substituent groups and variable structure; by adopting one raw material, high-quality product can be obtained through simple treatment, and the output is high; by adopting two different raw materials, the asymmetrical diaryl acetylene compound can be prepared.
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Page/Page column 0076; 0077; 0078; 0084; 0113
(2018/05/16)
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- Direct Synthesis of Symmetric Diarylethynes from Calcium Carbide and Arylboronic Acids/Esters
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A new methodology for the direct synthesis of symmetric diarylethynes from the reactions of calcium carbide with arylboronic acids/esters is described. Various symmetric diarylethynes were generated from the corresponding arylboronic acids/esters in satisfactory yield by using a palladium catalyst. The advantages of this protocol include the use of a readily available and easy-to-handle acetylene source, and a simple work-up procedure.
- Fu, Rugang,Li, Zheng
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p. 6648 - 6651
(2017/12/15)
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- Contorted aromatics: Via a palladium-catalyzed cyclopentannulation strategy
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We show that a new class of contorted polycyclic aromatic hydrocarbons (PAHs) containing five-membered rings can be prepared via a palladium-catalyzed cyclopentannulation followed by Scholl cyclodehydrogenation. The annulation chemistry can be accomplished between a di-arylethynylene and an appropriate aryl-dibromide to form 1,2,6,7-tetraarylcyclopenta[hi]aceanthrylenes and 1,2,6,7-tetraaryldicyclopenta[cd,jk]pyrenes. Scholl cyclodehydrogenation to close the externally fused aryl groups was accomplished only with properly arranged alkoxy substitutions and provides access to the pi-extended 2,7,13,18-tetraalkoxytetrabenzo[f,h,r,t]rubicenes and 2,7,13,18-tetraalkoxydibenzo[4,5:6,7]indeno[1,2,3-cd]dibenzo[4,5:6,7]indeno[1,2,3-jk]pyrenes. The final compounds each possess apparent [4]helicene-like arrangements with fused five-membered rings; however, only the 2,7,13,18-tetraalkoxytetrabenzo[f,h,r,t]rubicenes contort out of planarity owing to an additional [5]helicene like arrangement. Single crystal analysis of the contorted aromatic shows the PAHs stack in a lock-and-key like arrangement and pi-stack in a columnar arrangement. Solution-phase aggregation, as well as liquid crystalline mesophases, were found for derivatives with suitably attached solubilizing chains.
- Bheemireddy, Sambasiva R.,Ubaldo, Pamela C.,Finke, Aaron D.,Wang, Lichang,Plunkett, Kyle N.
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supporting information
p. 3963 - 3969
(2016/06/15)
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- Palladium-Catalyzed Domino Process: Synthesis of Symmetrical Diarylalkynes, cis- and trans-Alkenes using Lithium Acetylide as a Synthon
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An efficient domino protocol has been developed for the synthesis of symmetrical diarylalkynes. Notably, the method was successful in the presence of a palladium catalyst without the support of a copper co-catalyst. Significantly, the method enabled the use of the commercially available and cheap lithium acetylide ethylenediamine complex as a source of acetylene for the construction of dual C-C bonds, with a wide range of compatibility towards various substituents of the aryl bromides/iodides. Significantly, this protocol was successfully applied to the synthesis of cis- and trans-alkenes in a highly stereoselective manner in a sequential one-pot process.
- Krishna, Jonnada,Krishna Reddy, Alavala Gopi,Satyanarayana, Gedu
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p. 3597 - 3610
(2016/01/25)
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- Nickel-Catalyzed Insertion of Alkynes and Electron-Deficient Olefins into Unactivated sp3 C-H Bonds
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Insertion of unsaturated systems such as alkynes and olefins into unactivated sp3 C-H bonds remains an unexplored problem. We herein address this issue by successfully incorporating a wide variety of functionalized alkynes and electron-deficient olefins into the unactivated sp3 C-H bond of pivalic acid derivatives with excellent syn- and linear- selectivity. A strongly chelating 8-aminoquinoline directing group proved beneficial for these insertion reactions, while an air-stable and inexpensive NiII salt has been employed as the active catalyst. Unactive duty: A wide variety of functionalized alkynes and electron-deficient olefins has been incorporated into the unactivated sp3 C-H bond of pivalic acid derivatives with excellent syn and linear selectivity. A strongly chelating 8-aminoquinoline directing group proved beneficial for these insertion reactions, while an air-stable and inexpensive NiII salt was used as the active catalyst. EWG=electron-withdrawing group.
- Maity, Soham,Agasti, Soumitra,Earsad, Arif Mahammad,Hazra, Avijit,Maiti, Debabrata
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supporting information
p. 11320 - 11324
(2015/08/03)
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- Indole synthesis by rhodium(III)-catalyzed hydrazine-directed C-H activation: Redox-neutral and traceless by N-N bond cleavage
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Fishing for complements! There is an alternative to the useful Fischer indole synthesis. The new method utilizes the same retrosynthetic disconnection but is based on a RhIII-catalyzed directed C-H activation step and a successive coupling with alkynes. Copyright
- Zhao, Dongbing,Shi, Zhuangzhi,Glorius, Frank
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supporting information
p. 12426 - 12429
(2013/12/04)
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- A fluorogenic probe for the catalyst-free detection of azide-tagged molecules
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Fluorogenic reactions in which non- or weakly fluorescent reagents produce highly fluorescent products can be exploited to detect a broad range of compounds including biomolecules and materials. We describe a modified dibenzocyclooctyne that under catalyst-free conditions undergoes fast strain-promoted cycloadditions with azides to yield strongly fluorescent triazoles. The cycloaddition products are more than 1000-fold brighter compared to the starting cyclooctyne, exhibit large Stokes shift, and can be excited above 350 nm, which is required for many applications. Quantum mechanical calculations indicate that the fluorescence increase upon triazole formation is due to large differences in oscillator strengths of the S0 S 1 transitions in the planar C2v-symmetric starting material compared to the symmetry-broken and nonplanar cycloaddition products. The new fluorogenic probe was successfully employed for labeling of proteins modified by an azide moiety.
- Friscourt, Frederic,Fahrni, Christoph J.,Boons, Geert-Jan
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p. 18809 - 18815
(2013/01/15)
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- Synthesis of highly functionalized 9,10-phenanthrenequinones by oxidative coupling using MoCl5
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The strong oxidative power of molybdenum pentachloride gives rise to an efficient oxidative C-C bond formation of benzil derivatives to the corresponding 9,10-phenanthrenequinones. A highly complementary method to previous approaches was developed. The required derivatives are accessible in a modular fashion and in excellent yields. By this approach the orchid-derived natural product cypripediquinone A was synthesized for the first time.
- Trosien, Simon,Waldvogel, Siegfried R.
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supporting information; experimental part
p. 2976 - 2979
(2012/07/27)
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- Base-mediated selective synthesis of diversely substituted N-heterocyclic enamines and enaminones by the hydroamination of alkynes
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Regio- and stereoselective alkynylation of various N-heterocycles 1a-l using potassium and cesium salts in DMSO is described. Terminal alkynes 2a-k and internal alkynes 4a-f provided the kinetically stable Z-enamines 3a-l and 5a-i in good to excellent yields using KOH at 120 °C. Addition of heterocyclic amines to 1,3- and 1,4-diethynylbenzene 6a-b provided the mixture of E/Z isomers with KOH; however, with Cs2CO3 selectively Z-isomers 7ab-db were obtained by the hydroamination at one triple bond. This developed methodology also provides an easy and novel access for the synthesis of enaminones 10a-c. The detailed work also supports the formation of cis-isomer by preferential addition of o-haloarylalkynes followed by intramolecular C2 arylation in the copper-catalyzed tandem synthesis of indolo and pyrrolo[2,1-a]isoquinolines.
- Joshi, Megha,Patel, Monika,Tiwari, Rakesh,Verma, Akhilesh K.
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experimental part
p. 5633 - 5645
(2012/08/07)
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- One-pot synthesis of 1,4-diarylsubstituted 1,3-diynes from the sequential coupling reactions of aryl iodides and propiolic acid
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1,4-Disubstituted 1,3-dialkynes were obtained from the one-pot palladium/copper-catalyzed coupling reactions of aryl iodide and propiolic acid. The optimized catalytic system consisted of 5.0 mol % Pd(PPh3) 2Cl2, 10 mol % dppb, 10 mol % CuI, 2.4 equiv of DBU, and 1.2 equiv of K2CO3. The coupling reaction was carried out at 30 °C for 6 h and subsequently at 80 °C for 3 h.
- Kim, Yong,Park, Ahbyeol,Park, Kyungho,Lee, Sunwoo
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experimental part
p. 1766 - 1769
(2011/05/05)
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- Synthesis of symmetrical diarylalkyne from palladium-catalyzed decarboxylative couplings of propiolic acid and aryl bromides under water
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Symmetric diarylalkynes were obtained from the decarboxylative coupling reactions of aryl bromides and propiolic acid in water solvent condition. In the presence of phase transfer surfactant C18H37N(CH 3)3Cl, the catalytic system of both Pd(PPh 3)2Cl2/dppb and Pd(TPPMS)2Cl 2/TPPMS afforded the desired coupled products in good yields.
- Park, Kyungho,Bae, Goun,Park, Ahbyeol,Kim, Yong,Choe, Jaehoon,Song, Kwang Ho,Lee, Sunwoo
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experimental part
p. 576 - 580
(2011/03/18)
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- Allenes in asymmetric catalysis: Asymmetric ring opening of meso-epoxides catalyzed by allene-containing phosphine oxides
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(Chemical Equation Presented) Unsymmetrically substituted allenes (1,2-dienes) are inherently chiral and can be prepared in optically pure form. Nonetheless, to date the allene framework has not been incorporated into ligands for asymmetric catalysis. Since allenes project functionality differently than either tetrahedral carbon or chiral biaryls, they may create complementary chiral environments. This study demonstrates that optically active, C 2-symmetric allene-containing bisphosphine oxides can catalyze the addition of SiCl4 to meso-epoxides with high enantioselectivity. The epoxide opening likely involves generation of a Lewis acidic, cationic (bisphosphine oxide)SiCl3 complex. The fact that high asymmetric induction is observed suggests that allenes may represent a new platform for the development of ligands and catalysts for asymmetric synthesis.
- Pu, Xiaotao,Qi, Xiangbing,Ready, Joseph M.
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supporting information; experimental part
p. 10364 - 10365
(2009/12/03)
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- The use of calcium carbide in one-pot synthesis of symmetric diaryl ethynes
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An efficient Pd-catalyzed copper and amine free coupling reaction of acetylene and aryl bromides was achieved with calcium carbide as an acetylene source, using inorganic base and easily prepared, air-stable aminophosphine ligand in common organic solvents, providing symmetric diaryl ethynes in one-pot with yields ranged from moderate to excellent. The Royal Society of Chemistry 2006.
- Zhang, Weiwei,Wu, Huayue,Liu, Zhiqing,Zhong, Ping,Zhang, Lin,Huang, Xiaobo,Cheng, Jiang
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p. 4826 - 4828
(2007/10/03)
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- DICARBA-closo-DODECABORANE DERIVATIVES
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A medicament comprising as an active ingredient a compound or a physiologically acceptable salt thereof represented by general formula (I): wherein R1 represents a dicarba-closo-dodecaboran-yl which may be substituted with a lower alkyl group,
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- Alkyne metathesis with simple catalyst systems: High yield dimerization of propynylated aromatics; scope and limitations
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High yield dimerization of propynylated benzenes and propynylnaphthalene by a mixture of Mo(CO)6 and 4-chlorophenol at 140 °C in 1,2-dichlorobenzene is reported to give the corresponding disubstituted alkynes. The scope and limitation of the reaction and the influence of substitution pattern and substitution type are discussed. Oxygen or nitrogen carrying substrates metathesize in moderate to good yields and ortho-alkyl substituted examples form the respective tolanes very efficiently.
- Pschirer, Neil Gregory,Bunz, Uwe H. F.
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p. 2481 - 2484
(2007/10/03)
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- Oxidation of Aromatic Compounds. IV. Oxidation of Symmetrical Diarylacetylenes in the CF3COOH-CH2Cl2-PbO2 System. A New One-Pot Synthesis of 1,2,3,4-Tetraaryl-2-butene-1,4-diones
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Oxidation of symmetrical diarylacetylenes in the CF3COOH-CH2Cl2-PbO2 system (0-20 deg C, 1-3 h) yields 1,2,3,4-tetraaryl-2-butene-1,4-diones.According to (1)H NMR and GC-MS data the compounds synthesized have Z configuration.
- Rudenko, A. P.,Vasil'ev, A. V.
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p. 1360 - 1379
(2007/10/03)
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- Palladium(0) complex-catalyzed debrominative coupling of (tribromomethyl)- and (dibromomethyl)benzenes to diarylacetylenes and 1,2-diarylethenes
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Palladium(0)-triphenylphosphine complex-catalyzed debrominative coupling reaction of (tribromomethyl)benzenes gave diarylacetylenes or a mixture of (E)- and (Z)-α,β-dibromostilbenes depending upon the substrate and the solvent being used. On the other hand, (dibromomethyl)benzenes afforded (E)-stilbenes selectively under the same reaction conditions.
- Mataka,Liu,Tashiro
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p. 133 - 135
(2007/10/02)
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- Synthesis of symmetrical diarylalkynes by double stille coupling of bis(tributylstannyl)acetylene
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Treatment of bis(tributylstannyl)acetylene with two equivalents of an aryl iodide in the presence of tetrakis(triphenylphosphine)palladium (0) affords good yields of the symmetrical diarylalkyne. This approach provides a convenient and safe alternative to
- Cummins, Clark H.
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p. 857 - 860
(2007/10/02)
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