- Mild and Robust Stille Reactions in Water using Parts Per Million Levels of a Triphenylphosphine-Based Palladacycle
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An inexpensive and new triphenylphosphine-based palladacycle has been developed as a pre-catalyst, leading to highly effective Stille cross-coupling reactions in water under mild reaction conditions. Only 500–1000 ppm of Pd suffices for couplings involving a variety of aryl/heteroaryl halides with aryl/hetaryl stannanes. Several drug intermediates can be prepared using this catalyst in aqueous nanoreactors formed by 2 wt % Brij-30 in water.
- Takale, Balaram S.,Thakore, Ruchita R.,Casotti, Gianluca,Li, Xaiohan,Gallou, Fabrice,Lipshutz, Bruce H.
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supporting information
p. 4158 - 4163
(2021/02/01)
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- Development of oxathiino[6,5-b]pyridine 2,2-dioxide derivatives as selective inhibitors of tumor-related carbonic anhydrases IX and XII
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Oxathiino[6,5-b]pyridine 2,2-dioxides are identified as a new class of isoform-selective nanomolar inhibitors of tumor associated human carbonic anhydrases (hCA) IX and XII. At the same time they do not inhibit or poorly inhibit cytosolic isoforms hCA I and II. Oxathiino[6,5-b]pyridine 2,2-dioxides exhibited good antiproliferative properties on tumor cell lines MCF-7 (Human breast adenocarcinoma), A549 (human lung (alveolar) adenocarcinoma) and HeLa (epithelioid cervix carcinoma).
- Nocentini, Alessio,Supuran, Claudiu T.,?alubovskis, Raivis,Domra?eva, Ilona,Grandāne, Aiga
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supporting information
(2020/05/25)
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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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- Gold(i)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes
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Gold(i)-catalyzed cross-coupling reactions of aryldiazonium salts with organostannanes are described. This redox neutral strategy offers an efficient approach to diverse biaryls, vinyl arenes and arylacetylenes. Monitoring the reaction with NMR and ESI-MS provided strong evidence for the in situ formation of Ph3PAuIR (R = aryl, vinyl and alkynyl) species which is crucial for the activation of aryldiazonium salts.
- Akram, Manjur O.,Shinde, Popat S.,Chintawar, Chetan C.,Patil, Nitin T.
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supporting information
p. 2865 - 2869
(2018/05/03)
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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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- Controllable Stereoselective Synthesis of (Z)- and (E)-Homoallylic Alcohols Using a Palladium-Catalyzed Three-Component Reaction
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Diastereoselective synthesis of (Z)- and (E)-homoallylic alcohols using a Pd-catalyzed three-component reaction of 3-(pinacolatoboryl)allyl benzoates, aldehydes, and aryl stannanes was developed, which provides an alternative method for the allylboration of aldehydes using α, γ-diaryl-substituted allylboronates. Both sets of reaction conditions enable access to either (Z)- or (E)-homoallylic alcohols with good to high alkene stereocontrol. The present method showed good functional group compatibility and generality. Efficient chirality transfer reactions to afford enantioenriched (Z)- and (E)-homoallylic alcohols were also achieved.
- Horino, Yoshikazu,Sugata, Miki,Mutsuura, Itaru,Tomohara, Keisuke,Abe, Hitoshi
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supporting information
p. 5968 - 5971
(2017/11/10)
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- Pd-mediated cross-coupling of C-17 lithiated androst-16-en-3-ol-access to functionalized arylated steroid derivatives
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Herein, we report on Pd-mediated cross-coupling of vinyllithium steroids and aryl bromides to introduce various substituted aryls at C-17 of steroidal frameworks based on the structure of epi-androsterone. Compared to other C-C cross-couplings, this method turned out to be an easy and competitive access to biologically interesting C-17 modified steroids.
- Koch, Vanessa,Br?se, Stefan
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supporting information
p. 92 - 95
(2016/12/27)
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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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- Efficient one-pot cross-coupling of two aryl halides by stannylation/stille reaction in water under microwave irradiation
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A simple and highly efficient one-pot approach has been developed for the Pd(PPh3)4-catalyzed cross-coupling of two different aryl or heteroaryl bromides/iodides. This method involves the combined use of microwave irradiation and water as a single solvent to achieve sequential stannylation and Stille cross-coupling reactions, which allows rapid access to a wide variety of biaryls in good to high yields. Furthermore, utilizing this step-economical protocol, 2,5-dibromopyridine was iteratively diarylated and the Boscalid intermediate was also synthesized in a one-pot manner. Copyright
- Tan, Xin,Zhou, Zi Jie,Zhang, Jia Xin,Duan, Xin Hong
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supporting information
p. 5153 - 5157
(2014/09/29)
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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 46
(2010/07/10)
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- New and simple one-step cobalt-catalyzed preparation of functionalized arylstannanes from the corresponding aryl bromides or iodides
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The process for the preparation of functionalized arylstannanes from the corresponding aryl bromides or iodides was described. The corresponding arylstannane was detected by gas chromatography using an internal standard alkane. The two-step coupling react
- Gosmini, Corinne,Perichon, Jacques
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p. 216 - 217
(2007/10/03)
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- Layered double hydroxide supported nanopalladium catalyst for Heck-, Suzuki-, Sonogashira-, and Stille-type coupling reactions of chloroarenes
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Layered double hydroxide and Merrifield resin supported nanopalladium(0) catalysts are prepared by an exchange of PdCl42- followed by reduction and well characterized for the first time. The ligand-free heterogeneous layered double hydroxide supported nanopalladium (LDH-Pd0) catalyst using the basic LDH in place of basic ligands indeed exhibits higher activity and selectivity in the Heck olefination of electron-poor and electron-rich chloroarenes in nonaqueous ionic liquids (NAIL) over the homogeneous PdCl2 system. Using microwave irradiation, the rate of the Heck olefination reaction is accelerated, manifold with the highest turnover frequency ever recorded in the case of both electron-poor and electron-rich chloroarenes. The basic LDH-Pd0 shows a superior activity over a range of supported catalysts, from acidic to weakly basic Pd/C, Pd/SiO2, Pd/Al2O3, and resin-PdCl42- in the Heck olefination of deactivated electron-rich 4-chloroanisole. The use of LDH-Pd0 is extended to the Suzuki-, Sonogashira-, and Stille-type coupling reactions of chloroarenes in an effort to understand the scope and utility of the reaction. The catalyst is quantitatively recovered from the reaction by a simple filtration and reused for a number of cycles with almost consistent activity in all the coupling reactions. The heterogeneity studies provide an insight into mechanistic aspects of the Heck olefination reaction and evidence that the reaction proceeds on the surface of the nanopalladium particles of the heterogeneous catalyst. TEM images of the fresh and used catalyst indeed show that the nanostructured palladium supported on LDH remains unchanged at the end of the reaction, while the XPS and evolved gas detection by TGA-MS of the used catalyst identify ArPdX species on the heterogeneous surface. Thus, the ligand-free nanopalladium supported on LDH, synthesized by the simple protocol, displays superior activity over the other heterogeneous catalysts inclusive of nanopalladium in the C-C coupling reactions of chloroarenes.
- Choudary, Boyapati M.,Madhi, Sateesh,Chowdari, Naidu S.,Kantam, Mannepalli L.,Sreedhar, Bojja
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p. 14127 - 14136
(2007/10/03)
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- Palladium(II)- and rhodium(III)-catalyzed carbonylation reaction of aryltin compounds
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The Pd(II)- and Rh(III)-catalyzed carbonylation reaction of several aryltin compounds, i.e., tetraphenyltin (Ph4Sn), in acetonitrile (MeCN) and acetic acid was studied. The reaction of Ph4Sn with 1 atm of CO in the presence of a stoichiometric amount of Pd(II) salt was performed to confirm whether more than one of the four phenyl groups could be transferred to the products. To accelerate the carbonylation, LiCl was added, thus, producing benzophenone, benzoic acid, and a small amount of biphenyl as organic products, but only one of the four phenyl groups was transferred to the products. For the Rh(II)-mediated and -catalyzed carbonylation of aryltin compounds in MeCN, benzophenone was mainly produced together with benzoic acid and biphenyl. Seventy-five percent of the four phenyl groups were transferred to the products. The product yield was > 100% based on the amount of Rh(III) chloride used, showing that the Rh(III) salt itself worked as a catalyst without reoxidant addition. Thus, More than one of two, three, or four aryl groups of aryltin compounds, and almost all of them in some cases, could be transferred to the products in this catalytic carbonylation.
- Uemura,Ohe,Motofusa,Ohe
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p. 1343 - 1348
(2007/10/03)
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- SYNTHESIS OF ORGANOTRIALKYLSTANNANES. THE REACTION BETWEEN ORGANIC HALIDES AND HEXAALKYLDISTANNANES IN THE PRESENCE OF PALLADIUM COMPLEXES
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The aryl halides YC6H4X (X=Br or I) have been shown to react with the distannanes (R3Sn)2 (R=n-Bu or Me) in toluene in the presence of or to give the compounds YC6H4SnR3 for (a) R=n-Bu, Y=H, p-OMe, o-Me, p-Me, m-Cl, p-Cl, m-CN, p-COCH3 and m-NO2, and (b) R=Me, Y=H, p-OMe, p-Me, p-CN, p-COCH3, m-NO2 and p-NO2.Benzyl halides YC6H4CH2X (X=Cl or Br) similarly give YC6H4CH2SnR3 for (a) R=n-Bu, Y=H, m-OMe, p-OMe, m-Cl, m-CN, and m-NO2, and (b) R=Me, Y=m-Cl, m-CN, p-CN and m-NO2.These reactions are of special value as preparative procedures in cases in which Grignard or organolithium reagents cannot be used.Allyl chloride and bromide were likewise shown to react with (n-Bu3Sn)2 to give CH2=CHCH2SnBu3, but n-BuCl and n-BuBr gave only a trace of n-Bu4Sn.The mixed dimetallo species n-Bu3SnSiMe3 was shown to react with aryl bromides YC6H4Br (X=H, p-OMe, p-Me, or p-Cl) to give the arylsilicon compounds YC6H4SiMe3, with no aryltin products.
- Azizian, Hormoz,Eaborn, Colin,Pidcock, Alan
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