- An easily prepared, air and moisture stable, resin-bound palladium catalyst for Suzuki cross-coupling reactions
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An air and moisture stable polymer supported palladium catalyst easily prepared from a commercial available thiourea resin Deloxan THP was found to enable Suzuki cross-coupling reactions to be carried out in high yields and convenient manner.
- Zhang, Tony Y.,Allen, Matthew J.
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Read Online
- Biaryl Synthesis from Two Different Aryl Halides with Tri(2-furyl)germane
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(Matrix Presented) The coupling reaction of germanium compounds with aryl halides has been developed. The Pd(0)-catalyzed reaction of aryl halides with tri(2-furyl)germane provides aryltri(2-furyl)germanes in good yield. The cross-coupling reaction of aryltri(2-furyl)germanes with aryl halides is acheived. This allows facile synthesis of unsymmetrical biaryls from two different aryl halides.
- Nakamura, Tomoaki,Kinoshita, Hidenori,Shinokubo, Hiroshi,Oshima, Koichiro
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Read Online
- A Highly Active Cobalt Catalyst System for Kumada Biaryl Cross-Coupling
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A highly active cobalt catalyst system has been developed for the cross-coupling reactions of arylmagnesium reagents and aryl bromides. In the presence of 1 mol% CoCl 2, 2 mol% IPr·HCl and 2 mol% NaO t Bu, a wide range of (hetero)biaryls are prepared in 51-99% yields at room temperature within a short reaction time.
- Wu, Wenqin,Duong, Hung A.
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Read Online
- Decarbonylative Suzuki-Miyaura Cross-Coupling of Aroyl Chlorides
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Herein, we report a catalyst system for Pd-catalyzed decarbonylative Suzuki-Miyaura cross-coupling of aroyl chlorides with boronic acids to furnish biaryls. This strategy is suitable for a broad range of common aroyl chlorides and boronic acids. The synthetic utility is highlighted in the direct late-stage functionalization of pharmaceuticals and natural products capitalizing on the presence of carboxylic acid moiety. Extensive mechanistic and DFT studies provide key insight into the reaction mechanism and high decarbonylative cross-coupling selectivity.
- Zhou, Tongliang,Xie, Pei-Pei,Ji, Chong-Lei,Hong, Xin,Szostak, Michal
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supporting information
p. 6434 - 6440
(2020/09/02)
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- Nickel(II)/N-Heterocyclic Carbene Catalyzed Desulfinylative Arylation by C?S Cleavage of Aryl Sulfoxides with Phenylboronic Acids
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Suzuki-Miyaura coupling of haloarenes is the most widely used protocol for the synthesis of biphenyls. Organosulfur compounds are promising electrophiles since they are abundant in nature and versatile in organic synthesis. We report here the desulfinylative Suzuki-Miyaura coupling of aryl sulfoxides with phenylboronic acids using bench-stable nickel/5-(2,4,6-triisopropylphenyl)imidazolylidene[1,5-a]pyridines as the catalyst. The ligands are readily prepared from common commercial chemicals. The method is applicable to both symmetric and unsymmetric aryl sulfoxides, and a range of biphenyls bearing various functional groups were obtained in up to 94% yield. (Figure presented.).
- Yi, Xiaowen,Chen, Kai,Guo, Junjun,Chen, Wei,Chen, Wanzhi
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supporting information
p. 4373 - 4377
(2020/07/27)
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- Metal-Free Aryl Cross-Coupling Directed by Traceless Linkers
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The metal-free, highly selective synthesis of biaryls poses a major challenge in organic synthesis. The scope and mechanism of a promising new approach to (hetero)biaryls by the photochemical fusion of aryl substituents tethered to a traceless sulfonamide linker (photosplicing) are reported. Interrogating photosplicing with varying reaction conditions and comparison of diverse synthetic probes (40 examples, including a suite of heterocycles) showed that the reaction has a surprisingly broad scope and involves neither metals nor radicals. Quantum chemical calculations revealed that the C?C bond is formed by an intramolecular photochemical process that involves an excited singlet state and traversal of a five-membered transition state, and thus consistent ipso–ipso coupling results. These results demonstrate that photosplicing is a unique aryl cross-coupling method in the excited state that can be applied to synthesize a broad range of biaryls.
- Haensch, Veit G.,Neuwirth, Toni,Steinmetzer, Johannes,Kloss, Florian,Beckert, Rainer,Gr?fe, Stefanie,Kupfer, Stephan,Hertweck, Christian
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p. 16068 - 16073
(2019/11/28)
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- Organic transformations catalyzed by palladium nanoparticles on carbon nanomaterials
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Abstract: An efficient C–C bond coupling reactions (Suzuki–Miyaura and Glaser) catalyzed by PdO/GO nano-catalyst is presented. In addition, PdO/MWCNT nano-catalyst-mediated domino one-pot synthesis of 2-alkyl/2-aryl benzofurans has been accomplished from 2-iodophenols and terminal alkynes. The formation of benzofurans proceeds through intermolecular Sonogashira reaction followed by intramolecular nucleophilic addition of internal hydroxyl group onto the acetylenic bond. The catalyst PdO/GO has been reused successfully, with nearly no loss of activity up to 5 cycles. Graphical Abstract: : Synopsis: An efficient PdO/GO and PdO/MWCNT nanocatalysts have been developed for C–C coupling reactions like Suzuki and Glaser coupling reactions, multi-catalytic one-pot synthesis of 2-aryl, 2-alkyl benzofurans staring from 2-iodophenols and terminal alkynes. The protocol involves formation of benzofuran derivatives, i.e., Sonogashira reaction followed by 2-ethynyl phenol cyclization. [Figure not available: see fulltext.]
- Lakshminarayana, Bhairi,Mahendar, Lodi,Chakraborty, Jhonti,Satyanarayana, Gedu,Subrahmanyam, Ch
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- Regioselective Halogenation of Arenes and Heterocycles in Hexafluoroisopropanol
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Regioselective halogenation of arenes and heterocycles with N-halosuccinimides in fluorinated alcohols is disclosed. Under mild condition reactions, a wide diversity of halogenated arenes are obtained in good yields with high regioselectivity. Additionally, the versatility of the method is demonstrated by the development of one-pot sequential halogenation and halogenation-Suzuki cross-coupling reactions.
- Tang, Ren-Jin,Milcent, Thierry,Crousse, Benoit
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p. 930 - 938
(2018/01/28)
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- An immobilized symmetrical bis-(NHC) palladium complex as a highly efficient and recyclable Suzuki-Miyaura catalyst in aerobic aqueous media
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A bis-N-heterocyclic carbene (NHC) functionalized with chloropropyltriethoxysilane over silica was used to synthesize a well-defined immobilized palladium complex. This complex is a suitable and easily retrievable catalyst for Suzuki-Miyaura cross-coupling reactions under mild aqueous conditions. Excellent yields and conversions were obtained with low palladium loadings (down to 0.03 mol% Pd). The catalyst can be reused up to six cycles without the loss of its activity. The catalytic role of the NHC complex of palladium during coupling between bromobenzene and phenylboronic acid was investigated theoretically. The oxidative addition step is predicted to be endothermic in agreement with the experimental conditions.
- Begum, Tahshina,Mondal, Manoj,Borpuzari, Manash Protim,Kar, Rahul,Kalita, Golap,Gogoi, Pradip K.,Bora, Utpal
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supporting information
p. 539 - 546
(2017/01/10)
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- Suzuki-Miyaura cross-coupling reaction of aryl chlorides with aryl boronic acids catalyzed by a palladium dichloride adduct of N-diphenylphosphanyl-2-aminopyridine
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One palladium dichloride adduct of a phosphine-pyridine ligand N-diphenylphosphanyl-2-aminopyridine (L1) [(L1)PdCl2] (1) has been prepared and structurally characterized. Compound 1 can be used as an effective catalyst for the Suzuki-Miyaura cross-coupling reactions of unreactive aryl chlorides with aryl boronic acids, and worked much better than its mono- or bidentate phosphine ligands. The reactions with a wide scope of substrates proceeded to give desired products in good to excellent yields.
- Xu, Lin-Yan,Liu, Chun-Yu,Liu, Shi-Yuan,Ren, Zhi-Gang,Young, David James,Lang, Jian-Ping
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p. 3125 - 3132
(2017/05/08)
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- Iron(ii) triflate/N-heterocyclic carbene-catalysed cross-coupling of arylmagnesiums with aryl chlorides and tosylates
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In comparison to iron(ii) halides, iron(ii) triflate exhibits a greater resistance towards reduction by p-tolylmagnesium bromide. This knowledge has led to the development of an iron(ii) triflate/N-heterocyclic carbene-catalysed cross-coupling system of aryl Grignard reagents with aryl chlorides and tosylates with high efficiency, even surpassing that of previously reported catalyst systems employing strongly coordinating counterions in some cases.
- Chua, Yi-Yuan,Duong, Hung A.
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supporting information
p. 1466 - 1469
(2016/01/25)
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- Unified Protocol for Cobalt-Catalyzed Oxidative Assembly of Two Aryl Metal Reagents Using Oxygen as an Oxidant
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The first cobalt-catalyzed oxidative cross-coupling reaction of two aryl metal reagents is described. An equivalent amount of two aryl Grignard or lithium reagents, after mediation by an equivalent amount of simple ClTi(OEt)3, was facilely assembled under the catalysis of 1 mol % of CoCl2/10 mol % of DMPU using oxygen. The cross-couplings between various aryl metal reagents, especially between two structurally similar aryl Grignard reagents, proceeded smoothly and selectively and, thus, provided a highly general and efficient method for the construction of biaryl compounds.
- Liao, Lian-Yan,Liu, Kun-Ming,Duan, Xin-Fang
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p. 9856 - 9867
(2015/11/03)
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- Copper-catalyzed cross-coupling of aryl- and heteroaryltriethoxysilanes with aryl and heteroaryl iodides and bromides
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Copper(I)-catalyzed coupling of aryl- and heteroaryltriethoxysilanes with aryl and heteroaryl iodides is described. The transformation also proceeds with activated aryl bromides, but in this case it requires a stoichiometric amount of the catalyst for best product yields. The current reaction requires a P,N-based bidentate ligand for aryl-aryl coupling while it proceeds without external ligands for aryl-heteroaryl coupling to afford good product yields. The reaction protocol can also be applied to achieve biarylation of diiodoarenes in reasonable yields. Georg Thieme Verlag Stuttgart New York.
- Gurung, Santosh K.,Thapa, Surendra,Shrestha, Bijay,Giri, Ramesh
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p. 1933 - 1937
(2014/07/22)
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- Copper-catalyzed suzuki-miyaura coupling of arylboronate esters: Transmetalation with (PN)CuF and identification of intermediates
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An efficient CuI-catalyzed Suzuki-Miyaura reaction was developed for the coupling of aryl- and heteroarylboronate esters with aryl and heteroaryl iodides at low catalyst loadings (2 mol %). The reaction proceeds under ligand-free conditions for aryl-heteroaryl and heteroaryl-heteroaryl couplings. We also conducted the first detailed mechanistic studies by synthesizing [(PN-2)CuI]2, [(PN-2)CuF]2, and (PN-2)CuPh (PN-2 = o-(di-tert-butylphosphino)-N,N-dimethylaniline) and demonstrated that [(PN-2)CuF]2 is the species that undergoes transmetalation with arylboronate esters.
- Gurung, Santosh K.,Thapa, Surendra,Kafle, Arjun,Dickie, Diane A.,Giri, Ramesh
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supporting information
p. 1264 - 1267
(2014/03/21)
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- Iridium-promoted, palladium-catalyzed direct arylation of unactivated arenes
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A Pd-catalyzed cross-coupling reaction between Cp*(PMe 3)IrBn2 and aryl halides was developed. Examining the scope of this reaction led to the discovery that Cp*(PMe 3)IrMeCl activates C-H bonds on arene substrates that undergo subsequent Pd-catalyzed cross-coupling with aryl iodides. This Ir-promoted, Pd-catalyzed direct arylation is notable for its distal selectivity on substituted arenes lacking directing groups or a particular electronic bias.
- Durak, Landon J.,Lewis, Jared C.
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supporting information
p. 620 - 623
(2014/03/21)
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- Platinum-catalyzed C-H arylation of simple arenes
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This report describes the Na2PtCl4 catalyzed C-H arylation of arene substrates with diaryliodonium salts. The site selectivity of these reactions is predominantly controlled by steric factors. Remarkably, Na2PtCl4-catalyzed naphthalene arylation proceeds with opposite site selectivity compared to that obtained with Na2PdCl 4 as the catalyst. Preliminary mechanistic studies provide evidence for a PtII/PtIV catalytic cycle involving rate-limiting C-C bond-forming reductive elimination.
- Wagner, Anna M.,Hickman, Amanda J.,Sanford, Melanie S.
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supporting information
p. 15710 - 15713
(2013/11/06)
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- Direct catalytic cross-coupling of organolithium compounds
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Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern synthetic chemistry. However, the high reactivity and poor selectivity of common organolithium reagents have largely prohibited their use as a viable partner in direct catalytic cross-coupling. Here we report that in the presence of a Pd-phosphine catalyst, a wide range of alkyl-, aryl- and heteroaryl-lithium reagents undergo selective cross-coupling with aryl- and alkenyl-bromides. The process proceeds quickly under mild conditions (room temperature) and avoids the notorious lithium halogen exchange and homocoupling. The preparation of key alkyl-, aryl- and heterobiaryl intermediates reported here highlights the potential of these cross-coupling reactions for medicinal chemistry and material science.
- Giannerini, Massimo,Fananas-Mastral, Martin,Feringa, Ben L.
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p. 667 - 672
(2013/08/23)
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- Nickel-catalyzed Suzuki-Miyaura coupling of heteroaryl ethers with arylboronic acids
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Nickel-catalyzed Suzuki-Miyaura coupling of heteroaryl ethers with arylboronic acids was described. Selective activation of the phenol C-O bonds was achieved by converting them into the corresponding aryl 2,4-dimethoxy-1,3,5- triazine-6-yl ethers, in which aryl C-O bond could be selectively cleaved with inexpensive, air-stable NiCl2(dppf) as a catalyst. Coupling of these readily accessible heteroaryl ethers proved tolerant of extensive functional groups.
- Li, Xiao-Jian,Zhang, Jin-Ling,Geng, Yu,Jin, Zhong
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p. 5078 - 5084
(2013/06/27)
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- General and highly efficient fluorinated-N-heterocyclic carbene-based catalysts for the palladium-catalyzed Suzuki-Miyaura reaction
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A general and highly efficient trifluoromethylated-N-heterocyclic carbene (NHC)-based catalyst for the palladium-catalyzed Suzuki-Miyaura reaction was reported. In the presence of the catalyst, reactions of non-activated aryl chlorides and triflates with aryl boronic acids occurred at room temperature with good to excellent yields (63-98%). In addition, catalysts generated from a combination of Pd(OAc)2/imidazolium salt 6a is not only effective for the coupling of heteroaryl boronic acid with aryl halides and heteroaryl halides, but also efficient for coupling of other heteroaryl halides and heteroaryl boronic acids. Finally, the catalyst is highly effective for Suzuki-Miyaura reaction of aryl bromides and chlorides with 0.01-0.1 mol % loading if the temperature was raised at refluxed THF/H2O.
- Liu, Taoping,Zhao, Xiaoming,Shen, Qilong,Lu, Long
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supporting information; experimental part
p. 6535 - 6547
(2012/08/28)
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- Palladium membrane-installed microchannel devices for instantaneous Suzuki-Miyaura cross-coupling
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Instantaneous catalytic carbon-carbon bond-forming reactions were achieved in catalytic membrane-installed microchannel devices that have a polymeric palladium-complex membrane. The catalytic membrane-installed microchannel devices were provided inside the microchannels by means of coordinative and ionic molecular convolution at the interface between the organic and aqueous phases flowing laminarly, in which both non-crosslinked linear polymer ligands and palladium species dissolved. The palladium-catalyzed Suzuki-Miyaura reaction of aryl, heteroaryl, and alkenyl halides with arylboronic acids and sodium tetraarylborates was performed with the catalytic membrane-installed microchannel devices to give quantitative yields of biaryls, heterobiaryls, and aryl alkenes within 5 s of residence time in the defined channel region. These microchannel devices were applied to the instantaneous allylic aryla-tion reaction of allylic esters with aryl-boron reagents under microflow conditions to afford the corresponding coupling products within 1 s of residence time.
- Yamada, Yoichi M. A.,Watanabe, Toshihiro,Beppu, Tomohiko,Fukuyama, Naoshi,Torii, Kaoru,Uozumi, Yasuhiro
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experimental part
p. 11311 - 11319
(2010/11/04)
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- An efficient organocatalytic method for constructing biaryls through aromatic C-H activation
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The direct functionalization of C-H bonds has drawn the attention of chemists for almost a century. C-H activation has mainly been achieved through four metal-mediated pathways: oxidative addition, electrophilic substitution, σ-bond metathesis and metal-associated carbene/nitrene/oxo insertion. However, the identification of methods that do not require transition-metal catalysts is important because methods involving such catalysts are often expensive. Another advantage would be that the requirement to remove metallic impurities from products could be avoided, an important issue in the synthesis of pharmaceutical compounds. Here, we describe the identification of a cross-coupling between aryl iodides/bromides and the C-H bonds of arenes that is mediated solely by the presence of 1,10-phenanthroline as catalyst in the presence of KOt-Bu as a base. This apparently transition-metal-free process provides a new strategy with which to achieve direct C-H functionalization.
- Sun, Chang-Liang,Li, Hu,Yu, Da-Gang,Yu, Miao,Zhou, Xiao,Lu, Xing-Yu,Huang, Kun,Zheng, Shu-Fang,Li, Bi-Jie,Shi, Zhang-Jie
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experimental part
p. 1044 - 1049
(2011/09/20)
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- Nickel or Iron Catalysed Carbon-Carbon Coupling Reaction of Arylenes, Alkenes and Alkines
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Organozinc compounds of the type R1—Ar1—ZnY (1) can be reacted with different functionalized aryl halides R2—Ar2—X (2) in the presence of catalytic amounts of Ni or Fe in a polar solvent or solvent mixture to form polyfunctional biaryles of the type R1—Ar1—Ar2—R2 (3). Organozinc compounds of the type (1) can be represented by the transmetallation reaction of functionalized aryl magnesium halides or lithium aryl compounds with e.g. ZnBr2.
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Page/Page column 14
(2010/08/07)
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- Efficient synthesis of biaryls through the kumada reaction catalyzed by carbene adducts of cyclopalladated ferrocenylimine
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A series of carbene adducts of cyclopalladated ferrocenylimine were prepared, and evaluated in the cross-coupling reaction of aryl halides with Grignard reagents (the Kumada reaction). Complex d exhibited high catalytic activity for the coupling of aryl chlorides with sterically hindered Grignard reagents and the reaction tolerated various functional groups. A wide range of biaryls were efficiently obtained in good to excellent yields in the presence of 0.5 mol-% catalyst under mild reaction conditions.
- Ren, Gerui,Cui, Xiuling,Wu, Yangjie
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experimental part
p. 2372 - 2378
(2010/07/04)
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- Biaryl construction via Ni-catalyzed C-O activation of phenolic carboxylates
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Biaryl scaffolds were constructed via Ni-catalyzed aryl C-O activation by avoiding cleavage of the more reactive acyl C-O bond of aryl carboxylates. Now aryl esters, in general, can be successfully employed in cross-coupling reactions for the first time.
- Guan, Bing-Tao,Wang, Yang,Li, Bi-Jie,Yu, Da-Gang,Shi, Zhang-Jie
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supporting information; scheme or table
p. 14468 - 14470
(2009/02/08)
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- Palladium-catalyzed cross-coupling reaction using arylgermanium sesquioxide
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Powdery reagents obtained by complete alkaline hydrolysis of arylgermanium trichlorides were found to undergo the palladium-catalyzed cross-coupling reaction with aryl bromides and iodides in good yields. The reaction is performed in an aqueous medium taking sodium hydroxide as an activator. Some base-sensitive functionalities such as acetyl and trifluoromethyl groups survived the reaction.
- Endo, Mayuko,Fugami, Keigo,Enokido, Tatsuki,Sano, Hiroshi,Kosugi, Masanori
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p. 1025 - 1027
(2008/04/03)
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- Air-stable PinP(O)H as preligand for palladium-catalyzed Kumada couplings of unactivated tosylates
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Air-stable and easily accessible PinP(O)H enables highly efficient palladium-catalyzed Kumada cross-coupling reactions of aryl tosylates. The in situ generated catalyst proved applicable not only to electron-rich and electron-poor carbocyclic tosylates but also to heterocyclic tosylates, such as pyridine and quinoline derivatives. The results described herein constitute the first use of air-stable secondary phosphine oxides as preligands for transition-metal-catalyzed coupling reactions between organometallic species and tosylates.
- Ackermann, Lutz,Althammer, Andreas
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p. 3457 - 3460
(2007/10/03)
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- Nickel(0)/imidazolium carbene catalyst system for efficient cross-coupling of aryl bromides and chlorides with organomanganese reagents
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N,N′-Bis(2,6-diisopropylphenyl)imidazolium chloride associated with nickel(II) acetylacetonate (3-5 mol%) was used as catalyst to efficiently cross-couple functionalized aryl bromides with organomanganese reagents. The reactions were performed between 0°C and room temperature, giving unsymmetrical biaryls in 0.25 to 24 h with 52 to 100% yields for isolated materials. Aryl chlorides showed slightly diminished reactivity in Ni/2 IPr-catalyzed cross-couplings and good yields could only be attained with activated or neutral substrates.
- Leleu, Anne,Fort, Yves,Schneider, Raphael
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p. 1086 - 1092
(2007/10/03)
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- Development of a continuous-flow system for catalysis with palladium(0) particles
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Heterogeneous catalysis for organic synthesis under continuous-flow conditions becomes possible by a new reactor-based approach. Continuous-flow reactors with a monolithic glass/polymer composite interior are loaded with palladium particles by ion exchange followed by reduction. When incorporated into a continuous-flow setup (PASSflow) this reactor allows the transfer-hydrogenation of alkenes, alkynes, nitro-substituted aromatic compounds and benzyl ethers in the flow-through mode. In addition, the activity of the catalysts is well suited to achieve Suzuki, Sonogashira and Heck cross-coupling reactions in the absence of phosphanes or any other ligands, resulting in a greatly simplified purification. As an extension to this concept a bifunctional support was prepared inside the reactor consisting of Pd particles and an ion-exchange group (hydroxide form). In the Suzuki-Miyaura reaction the reactor serves as a base for immobilisation and activation of the boronic acid as boronate and as a catalyst for promoting the C-C coupling reaction under continuous-flow conditions. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- Solodenko, Wladimir,Wen, Hongliang,Leue, Stefanie,Stuhlmann, Friedrich,Sourkouni-Argirusi, Georgia,Jas, Gerhard,Schoenfeld, Hagen,Kunz, Ulrich,Kirschning, Andreas
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p. 3601 - 3610
(2007/10/03)
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- Microwave-assisted Suzuki-Miyaura reactions with an insoluble pyridine-aldoxime Pd-catalyst
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The preparation of a solid Pd(II)-precatalyst and its use in microwave-assisted Suzuki-Miyaura reactions in water is described. The precatalyst is obtained by treatment of 4-pyridine-aldoxime with Na 2PdCl4 and is insoluble in organic solvents as well as in water. Its robustness under microwave conditions and its insolubility allows simple reuse in 'teabags'.
- Solodenko, Wladimir,Sch?n, Uwe,Messinger, Josef,Glinschert, Anja,Kirschning, Andreas
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p. 1699 - 1702
(2007/10/03)
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- Highly Efficient Palladium-Catalyzed Boronic Acid Coupling Reactions in Water: Scope and Limitations
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The "ligandless" palladium acetate-catalyzed Suzuki cross-coupling reaction of ArX with aryl- and vinylboronic acids in water without organic cosolvent in the presence of tetrabutylammonium bromide is reported. Aryl bromides give high yields and considerably accelerate the coupling. A wide variety of functional groups can be tolerated. Aryl iodides, however, give incomplete conversion and aryl triflate coupling shows no improvement over reported conditions.
- Badone,Baroni,Cardamone,Ielmini,Guzzi
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p. 7170 - 7173
(2007/10/03)
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