- Synthesis of Long-Chain Alkanoyl Benzenes by an Aluminum(III) Chloride-Catalyzed Destannylative Acylation Reaction
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This paper describes the facile synthesis of haloaryl compounds with long-chain alkanoyl substituents by the destannylative acylation of haloaryls bearing tri-n-butyltin (Bu3Sn) substituents. The method allows the synthesis of many important synthons for novel functional materials in a highly efficient manner. The halo-tri-n-butyltin benzenes are obtained by the lithium-halogen exchange of commercially available bis-haloarenes and the subsequent reaction with Bu3SnCl. Under typical Friedel-Crafts conditions, i.e., the presence of an acid chloride and AlCl3, the haloaryls are acylated through destannylation. The reactions proceed fast (5 min) at low temperatures and thus are compatible with aromatic halogen substituents. Furthermore, the method is applicable topara-,meta-, andortho-substitution and larger systems, as demonstrated for biphenyls. The generated tin byproducts were efficiently removed by trapping with silica/KF filtration, and most long-chain haloaryls were obtained chromatography-free. Molecular structures of several products were determined by X-ray single-crystal diffraction, and the crystal packing was investigated by mapping Hirshfeld surfaces onto individual molecules. A feasible reaction mechanism for the destannylative acylation reaction is proposed and supported through density functional theory (DFT) calculations. DFT results in combination with NMR-scale control experiments unambiguously demonstrate the importance of the tin substituent as a leaving group, which enables the acylation.
- Roemer, Max,Keaveney, Sinead T.,Proschogo, Nicholas
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p. 9007 - 9022
(2021/07/20)
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- Oxidative Addition of Alkenyl and Alkynyl Iodides to a AuI Complex
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The first isolated examples of intermolecular oxidative addition of alkenyl and alkynyl iodides to AuI are reported. Using a 5,5′-difluoro-2,2′-bipyridyl ligated complex, oxidative addition of geometrically defined alkenyl iodides occurs readily, reversibly and stereospecifically to give alkenyl-AuIII complexes. Conversely, reversible alkynyl iodide oxidative addition generates bimetallic complexes containing both AuIII and AuI centers. Stoichiometric studies show that both new initiation modes can form the basis for the development of C?C bond forming cross-couplings.
- Bower, John F.,Cadge, Jamie A.,Russell, Christopher A.,Sparkes, Hazel A.
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supporting information
p. 6617 - 6621
(2020/03/13)
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- Nickel-catalyzed decarbonylative stannylation of acyl fluorides under ligand-free conditions
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Nickel-catalyzed decarbonylative stannylation of acyl fluorides under ligand-free conditions was disclosed. A variety of aromatic acyl fluorides are capable of reacting with silylstannanes in the presence of cesium fluoride. A one-pot decarbonylative stannylation/Migita-Kosugi-Stille reaction of benzoyl fluoride, giving rise to the direct formation of the corresponding cross-coupled products, further demonstrated the synthetic utility of the present method. This newly developed methodology with a good functional-group compatibility via C-F bond cleavage and C-Sn bond formation under nickel catalysis opens a new area for the functionalization of acyl fluorides in terms of carbon-heteroatom bond formation.
- Wang, Xiu,Wang, Zhenhua,Liu, Li,Asanuma, Yuya,Nishihara, Yasushi
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- Method for converting substituted sodium aryl sulfonate to aryl tri-n-butyltin
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The invention discloses a method for converting substituted sodium acryl sulfonate to aryl tri-n-butyltin. The synthetic method of the aryl tri-n-butyltin compound comprises the following steps: uniformly mixing sodium aryl sulfonate, silver carbonate, bis(tri-tert-butylphosphine)palladium, and hexabutyldistannane in a solvent, reacting for 1 to 8 hours at 80 to 140 DEG C, and after the reaction is ended, concentrating; and performing the column chromatography, and obtaining a pure aryl tri-n-butyltin product. The adopted raw material is sodium aryl sulfonate which is significant in supplementation, wide in source, cheap and easy to obtain compared with the existing method adopting aromatic halides as a raw material. The reaction in the invention has good tolerance and universality for a functional group, and the substituent group can be hydrogen, methyl, tertiary butyl, fluorine, chlorine, bromine, cyanogroup, trifluoromethyl, nitro, acetyl or carbethoxy.
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Paragraph 0058-0062
(2018/12/14)
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- Synthesis of arylstannanes by palladium-catalyzed desulfitative coupling reaction of sodium arylsulfinates with distannanes
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A novel Pd-catalyzed desulfitative cross-coupling reaction of sodium arylsulfinates with hexaalkyl distannanes is realized, allowing the facile synthesis of functionalized arylstannanes with moderate to excellent yields. The successful implement of gram-scale synthesis and tandem Stille coupling reaction demonstrates the potential applications of this method in organic synthesis.
- Lian, Chang,Yue, Guanglu,Zhang, Haonan,Wei, Liyan,Liu, Danyang,Liu, Sichen,Fang, Huayi,Qiu, Di
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supporting information
p. 4019 - 4023
(2018/10/04)
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- Catalytic Ester to Stannane Functional Group Interconversion via Decarbonylative Cross-Coupling of Methyl Esters
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An unprecedented conversion of methyl esters to stannanes was realized, providing access to a series of arylstannanes via nickel catalysis. Various common esters including ethyl, cyclohexyl, benzyl, and phenyl esters can undergo the newly developed decarbonylative stannylation reaction. The reaction shows broad substrate scope, can differentiate between different types of esters, and if applied in consecutive fashion, allows the transformation of methyl esters into aryl fluorides or biaryls via fluororination or arylation.
- Yue, Huifeng,Zhu, Chen,Rueping, Magnus
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supporting information
p. 385 - 388
(2018/01/27)
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- Stannylation of Aryl Halides, Stille Cross-Coupling, and One-Pot, Two-Step Stannylation/Stille Cross-Coupling Reactions under Solvent-Free Conditions
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Solvent-free protocols for palladium-catalyzed stannylation of aryl halides, Stille cross-coupling, and one-pot, two-step stannylation/Stille cross-coupling (SSC) are reported for the first time. (Het)aryl halides bearing acceptor, donor, as well as sterically demanding substituents are stannylated and/or coupled in high yields. The reactions are catalyzed by conventional palladium(II) acetate/PCy3 [Pd(OAc)2/PCy3] under air, using available base CsF, and without the use of high purity reagents. The developed synthetic procedures are versatile, robust, and easily scalable. The absence of solvent, and the elimination of isolation procedures of aryl stannanes makes the SSC protocol simple, step economical, and highly efficient for the synthesis of biaryls in a one-pot two-step procedure.
- Gribanov, Pavel S.,Golenko, Yulia D.,Topchiy, Maxim A.,Minaeva, Lidiya I.,Asachenko, Andrey F.,Nechaev, Mikhail S.
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supporting information
p. 120 - 125
(2018/01/17)
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- Stille and Suzuki Cross-Coupling Reactions as Versatile Tools for Modifications at C-17 of Steroidal Skeletons – A Comprehensive Study
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Herein, we report on a comparative Stille and Suzuki cross-coupling study of steroidal vinyl (pseudo)halides with different boronic acids and tributyltin organyls. Furthermore, we have investigated the “inverse” case of those cross-coupling reactions, i.e., the reaction of a steroidal vinylpinacolatoborane or a tributyltin steroid with various bromides. The development of both methods allows the introduction of different residues at C-17 of steroid skeletons providing access to a broad variety of steroid analogues which are of high interest for biological screenings or natural product synthesis. (Figure presented.).
- Koch, Vanessa,Nieger, Martin,Br?se, Stefan
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supporting information
p. 832 - 840
(2017/03/11)
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- METHOD FOR PRODUCING 14 GROUP METAL LITHIUM COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for quantitatively producing a group 14 metal lithium compound under a mild condition. SOLUTION: The method for producing a group 14 metal lithium compound represented by formula (4): R4-nMLin comprises reacting a compound represented by formula (1): R4-nMXn and lithium in the presence of a polycyclic aromatic compound represented by formula (2) or formula (3). [In formula (1) and formula (2), R is a hydrocarbon group; M is a metal atom selected from Si, Ge and Sn; X is a halogen atom or R3M- (R and M are the same as mentioned above); and n is 1 or 2] and [R1 is H or a hydrocarbon group; and m is an integer of 0 to 5.] SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0085-0086; 0088
(2016/10/31)
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- Stannyl-Lithium: A Facile and Efficient Synthesis Facilitating Further Applications
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We have developed a highly efficient, practical, polycyclic aromatic hydrocarbon (PAH)-catalyzed synthesis of stannyl lithium (Sn-Li), in which the tin resource (stannyl chloride or distannyl) is rapidly and quantitatively transformed into Sn-Li reagent at room temperature without formation of any (toxic) byproducts. The resulting Sn-Li reagent can be stored at ambient temperature for months and shows high reactivity toward various substrates, with quantitative atom efficiency.
- Wang, Dong-Yu,Wang, Chao,Uchiyama, Masanobu
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supporting information
p. 10488 - 10491
(2015/09/28)
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- A Sn atom-economical approach toward arylstannanes: Ni-catalysed stannylation of aryl halides using Bu3SnOMe
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Stannylation of carbon-halogen bonds is one of the most promising and straightforward approaches for the preparation of organostannane compounds. Although a wide variety of methods are now available, all protocols require the use of highly nucleophilic organometals or wasteful stannyl sources like distannanes. Here, we report a new nickel-catalysed stannylation of aryl and alkenyl-halides using Bu3SnOMe as a stannyl source to afford aryl and vinyl-stannanes, respectively. This method enables the stannylation of not only bromides, but also chlorides and triflates to furnish functionalized aryl- and alkenyl-stannanes without the release of wasteful and toxic stannyl byproducts.
- Komeyama, Kimihiro,Asakura, Ryota,Takaki, Ken
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supporting information
p. 8713 - 8716
(2015/08/24)
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- Simple preparation of aryltributylstannanes and its application to one-pot synthesis of diaryl ketones
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Transfer of aryl group from boron to tin can be achieved by simple treatment of arylboronic acids with tributyltin methoxide at 100 °C for 1 h under neat conditions. The resulting aryltributylstannanes are applicable to one-pot synthesis of diaryl ketones. Thus, Pd-catalyzed cross-coupling reaction with aroyl chlorides is allowed to proceed without isolation step to produce the corresponding diaryl ketones in good to high yields.
- Oikawa, Asuka,Kindaichi, Gan,Shimotori, Yasutaka,Okimoto, Mitsuhiro,Hoshi, Masayuki
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supporting information
p. 1705 - 1711
(2015/03/30)
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- FLUORINATION OF ORGANIC COMPOUNDS
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Methods for fluorinating organic compounds are described herein.
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Page/Page column 33
(2010/07/10)
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- Highly fluorinated dithieno[3,2-b:2′,3′-d]phospholes with stabilized LUMO levels
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A series of dithieno[3,2-b:2′,3′-d]phospholes with a perfluorophenyl substituent at the phosphorus center has been synthesized. Further cross-coupling reactions with additional fluorinated phenyl groups afforded extended conjugated materials with differen
- Ren, Yi,Dienes, Yvonne,Hettel, Sonja,Parvez, Masood,Hoge, Berthold,Baumgartner, Thomas
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p. 734 - 740
(2009/06/20)
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- PYRIDINE ANCHORS FOR HMG-COA REDUCTASE INHIBITORS
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Compounds which are useful as inhibitors of cholesterol biosynthesis and thus as hypocholesterolemic agents are provided which have a quinoline or a pyridine anchor attached by means of a linker to a binding domain sidechain, which compounds inhibit the e
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