- Preparation of Alkyl Indium Reagents by Iodine-Catalyzed Direct Indium Insertion and Their Applications in Cross-Coupling Reactions
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An efficient method for the synthesis of alkyl indium reagent by means of an iodine-catalyzed direct indium insertion into alkyl iodide in THF is reported. The thus-generated alkyl indium reagents effectively underwent Pd-catalyzed cross-coupling reactions with various aryl halides, exhibiting good compatibility to a variety of sensitive functional groups. By replacing THF with DMA and using 0.75 equiv of iodine, less reactive alkyl bromide could be used as substrate for indium insertion with equal ease.
- Zhi, Man-Ling,Chen, Bing-Zhi,Deng, Wei,Chu, Xue-Qiang,Loh, Teck-Peng,Shen, Zhi-Liang
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- Highly efficient, general procedure for the preparation of alkylzinc reagents from unactivated alkyl bromides and chlorides
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(Matrix presented) Alkylzinc bromides have been efficiently prepared by the direct insertion of zinc metal (dust, powder, granule, shot), activated with 1-5 mol % I2, into alkyl bromides in a polar aprotic solvent. The zinc reagents thus formed undergo Ni- and Pd-catalyzed cross-coupling with aryl halides to produce functionalized alkylarenes in excellent yields.
- Huo, Shouquan
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- Cesium carbonate-catalyzed indium insertion into alkyl iodides and their synthetic utilities in cross-coupling reactions
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A catalytic amount of cesium carbonate (10?mol%) was found to be capable of effectively catalyzing the insertion of indium powder into alkyl iodides. The thus-generated alkyl indium reagents could readily undergo palladium-catalyzed cross-coupling reactions with a wide variety of aryl halides, showing compatibility to a range of important functional groups.
- Feng, Xue-Xin,Wu, Zhen,Wang, Qing-Dong,Chen, Bing-Zhi,Rao, Weidong,Yang, Jin-Ming,Shen, Zhi-Liang
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- Copper(II)-catalyzed preparation of alkylindium compounds and applications in cross-coupling reactions both in aqueous media
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An efficient water-based method for the synthesis of alkylindium compound in the presence of a catalytic amount of cheap and readily available CuSO4·5H2O (10 mol%) was developed. The thus-generated alkylindium compounds effectively underwent palladium-catalyzed cross-coupling reactions with a myriad of aryl halides in aqueous media, leading to the cross-coupled products in modest to high yields. The mildness of the formed alkyl organometallics allowed the tolerance to various important functional groups incorporated in both substrates of alkyl iodides and aryl halides.
- Wang, Peng,Chen, Bing-Zhi,Guo, Yi-Cong,Rao, Weidong,Shen, Zhi-Liang
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- Cobalt(II)-catalyzed preparation of alkylindium reagents and applications in cross-coupling with aryl halides
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The direct insertion of indium powder into alkyl iodides was found to be efficiently catalyzed by a catalytic amount of cobalt(II) bromide (10 mol%). Upon subjection of the thus-formed alkylindium compounds to palladium-catalyzed cross-coupling reactions with a wide range of aryl halides, a series of cross-coupled products could be obtained in moderate to good yields with the tolerance to many important functional groups.
- Wang, Peng,Song, Xuan-Di,Chen, Bing-Zhi,Rao, Weidong,Shen, Zhi-Liang
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- ADDITION OF ARYL RADICALS GENERATED FROM ELECTROCHEMICAL REDUCTION OF ARYL HALIDES ON CARBON-CARBON DOUBLE BONDS.
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Aryl radicals generated by electrochemical reduction of aryl halides in aprotic medium react with styrene and its derivatives to give arylated addition compounds.
- Chami, Zoubida,Gareil, Monique,Pinson, Jean,Saveant, Jean-Michel,Thiebault, Andre
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- Photoredox Heterobimetallic Dual Catalysis Using Engineered Covalent Organic Frameworks
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The functionalization of an imine-based layered covalent organic framework (COF), containing phenanthroline units as ligands, has allowed the obtention of a heterobimetallated material. Photoactive Ir and Ni fragments were immobilized within the porous structure of the COF, enabling heterogeneous light-mediated Csp3-Csp2cross-couplings. As radical precursors, potassium benzyl- and alkoxy-trifluoroborates, organic silicates, and proline derivatives were employed, which brings out the good versatility ofIr,Ni@Phen-COF. Moreover, in all the studied cases, an enhanced activity and stability have been observed in comparison with analogous homogenous systems.
- Alemán, José,Imaz, Inhar,López-Magano, Alberto,Mas-Ballesté, Rubén,Maspoch, Daniel,Ortín-Rubio, Borja
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p. 12344 - 12354
(2021/10/12)
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- Electrochemically Enabled, Nickel-Catalyzed Dehydroxylative Cross-Coupling of Alcohols with Aryl Halides
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As alcohols are ubiquitous throughout chemical science, this functional group represents a highly attractive starting material for forging new C-C bonds. Here, we demonstrate that the combination of anodic preparation of the alkoxy triphenylphosphonium ion and nickel-catalyzed cathodic reductive cross-coupling provides an efficient method to construct C(sp2)-C(sp3) bonds, in which free alcohols and aryl bromides - both readily available chemicals - can be directly used as coupling partners. This nickel-catalyzed paired electrolysis reaction features a broad substrate scope bearing a wide gamut of functionalities, which was illustrated by the late-stage arylation of several structurally complex natural products and pharmaceuticals.
- Li, Zijian,Sun, Wenxuan,Wang, Xianxu,Li, Luyang,Zhang, Yong,Li, Chao
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supporting information
p. 3536 - 3543
(2021/03/08)
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- Photo-catalytic preparation method of bibenzyl compounds
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The invention relates to a preparation method of bibenzyl compounds. A compound represented by a formula (A) and a compound represented by a formula (C) carry out reactions under the action of an organic tungsten catalyst and an alkali in the presence of light to generate bibenzyl compounds represented by the formula (B). The method is simple and is easy to operate. The yield is high, and the application range is wide. Moreover, the invention also provides an application of a tungsten complex in organic chemical reactions as a photocatalyst.
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Paragraph 0079-0081
(2020/02/27)
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- One-Pot Electrochemical Nickel-Catalyzed Decarboxylative Sp2-Sp3 Cross-Coupling
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A one-pot electrochemical nickel-catalyzed decarboxylative sp2-sp3 cross-coupling reaction has been developed using redox-active esters prepared in situ from alkyl carboxylates and N-hydroxyphthalimide tetramethyluronium hexafluorophosphate (PITU). This undivided cell one-pot method enables C-C bond formation using inexpensive, benchtop-stable reagents with isolated yields up to 95% with good functional group tolerance, which includes nitrile, ketone, ester, alkene and selectivity over other aromatic halogens.
- Koyanagi, Takaoki,Herath, Ananda,Chong, Ashley,Ratnikov, Maxim,Valiere, Andrew,Chang, Jim,Molteni, Valentina,Loren, Jon
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supporting information
p. 816 - 820
(2019/01/30)
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- Bis(bipyridine) ruthenium(ii) bis(phosphido) metalloligand: Synthesis of heterometallic complexes and application to catalytic (E)-selective alkyne semi-hydrogenation
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The first phosphido derivative of the bis(bipyridine) ruthenium(ii) fragment, cis-[(bpy)2Ru(PPh2)2] ([RuP2]), has been developed and applied as a P-donor metalloligand to form new Ru-Rh, Ru-Ir and Ru2Cu2 heterometallic complexes. The Ru-Ir hydride complex [([RuP2])IrH(NCMe)3][BF4]2 exhibits significant catalytic activity for (E)-selective semi-hydrogenation of alkynes.
- Takemoto, Shin,Kitamura, Manami,Saruwatari, Shuhei,Isono, Atsutaka,Takada, Yoko,Nishimori, Rie,Tsujiwaki, Mina,Sakaue, Naoki,Matsuzaka, Hiroyuki
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supporting information
p. 1161 - 1165
(2019/01/28)
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- Application of novel coupling reaction to preparing carbon-carbon bond structured compounds
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The invention relates to application of a novel coupling reaction to preparing carbon-carbon bond structured compounds and mainly provides a reaction between alkyl indium compounds and halides. The reaction between the alkyl indium compounds and the halides can produce corresponding carbon-carbon structured products. The novel coupling reaction is high in process yield, broad in functional group tolerance and good in compatibility.
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Paragraph 0074-0078
(2019/06/30)
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- Structure-activity relationship studies of the lipophilic tail region of sphingosine kinase 2 inhibitors
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Sphingosine-1-phosphate (S1P) is a ubiquitous, endogenous small molecule that is synthesized by two isoforms of sphingosine kinase (SphK1 and 2). Intervention of the S1P signaling pathway has attracted significant attention because alteration of S1P levels is linked to several disease states including cancer, fibrosis, and sickle cell disease. While intense investigations have focused on developing SphK1 inhibitors, only a limited number of SphK2-selective agents have been reported. Herein, we report our investigations on the structure-activity relationship studies of the lipophilic tail region of SLR080811, a SphK2-selective inhibitor. Our studies demonstrate that the internal phenyl ring is a key structural feature that is essential in the SLR080811 scaffold. Further, we show the dependence of SphK2 activity and selectivity on alkyl tail length, suggesting a larger lipid binding pocket in SphK2 compared to SphK1.
- Congdon, Molly D.,Childress, Elizabeth S.,Patwardhan, Neeraj N.,Gumkowski, James,Morris, Emily A.,Kharel, Yugesh,Lynch, Kevin R.,Santos, Webster L.
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p. 4956 - 4960
(2015/10/28)
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- Catalytic, oxidant-free, direct olefination of alcohols using Wittig reagents
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Reported here is the catalytic, acceptorless coupling of alcohols with in situ generated, non-stabilized phosphonium ylides to form olefins as major products. The reaction uses low catalyst loadings and does not require added oxidants. Hydrogenation of the product is minimized and the reaction leads to Z (aliphatic) or E (benzylic) stereospecificity.
- Khaskin,Milstein
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supporting information
p. 9002 - 9005
(2015/05/27)
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- Development of the direct Suzuki-Miyaura cross-coupling of primary B-alkyl MIDA-boronates and aryl bromides
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The development of a palladium-catalyzed sp3-sp2 Suzuki-Miyaura cross-coupling of B-alkyl-N-methyliminodiacetyl (B-alkyl MIDA) boronates and (hetero)aryl bromides is reported. This transformation is tolerant of a variety of functional groups (F, NO2, CN, Cl, COCH3, and CHO). B-Alkyl MIDA boronates allow an efficient cross-coupling reaction directed toward the synthesis of unsymmetrical methylene diaryls as well as alkylated arenes in good to excellent yields.
- St. Denis, Jeffrey D.,Scully, Conor C. G.,Lee, C. Frank,Yudin, Andrei K.
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supporting information
p. 1338 - 1341
(2014/04/03)
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- Photoreduction of aliphatic and aromatic thioketals: New access to the reduction of carbonyl groups by a desulfurization chain process
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Aromatic and aliphatic ketones can be converted to methylene groups by desulfurization of the corresponding dithioketals in moderate to good yields. The reaction proceeds by photoinduced electron transfer from tert-BuOK in the presence of 1,4-dicyclohexadiene as hydrogen atom donor. The diene is able to trigger and keep a chain process by hydrogen transfer-proton transfer reactions.
- Oksdath-Mansilla, Gabriela,Argüello, Juan E.,Pe?é?ory, Alicia B.
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p. 1515 - 1518
(2013/03/14)
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- Preparation of functionalized organoindium reagents by means of magnesium insertion into organic halides in the presence of InCl3 at room temperature
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Magnesium, indium, palladium: An efficient one-pot procedure for the direct preparation of triorganoindium reagents from organic halides by means of magnesium insertion in the presence of InCl3 and LiCl is reported (see scheme). The organoindium reagents are obtained in good yields from functionalized aryl, heteroaryl, and alkyl bromides and benzyl chlorides at 25 °C in THF within 4h. Moreover, the resulting organoindium reagents could be efficiently used as reagents in Pd-catalyzed cross-coupling reactions with a wide functional group tolerance. Copyright
- Bernhardt, Sebastian,Shen, Zhi-Liang,Knochel, Paul
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supporting information
p. 828 - 833
(2013/02/23)
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- Aryl-aryl interactions as directing motifs in the stereodivergent iron-catalyzed hydrosilylation of internal alkynes
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The defined Fe hydride complex FeH(CO)(NO)(Ph3P)2 is highly active as a catalyst for selective hydrosilylation of internal alkynes to vinylsilanes. Depending on the silane employed either E- or Z-selective hydrosilylation products were formed in excellent yields and good to excellent stereoselectivities.
- Belger, Christian,Plietker, Bernd
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p. 5419 - 5421
(2012/07/03)
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- DABO boronates: Stable heterocyclic boronic acid complexes for use in suzuki-miyaura cross-coupling reactions
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Diethanolamine-complexed heterocyclic boronic acids (DABO boronates) are air-stable reagents that can be used directly in Suzuki-Miyaura reactions in the presence of water or a protic co-solvent. Interestingly, heterocyclic DABO boronates can be stored for extended periods of time at room temperature with no noticeable degradation, unlike their boronic acid counterparts. Heterocyclic DABO boronates constitute an operationally simple and efficient alternative to other boronic acid derivatives as coupling partners in palladium-catalyzed cross-coupling reactions under standard Suzuki-Miyaura conditions. Georg Thieme Verlag Stuttgart - New York.
- Reilly, Maureen K.,Rychnovsky, Scott D.
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supporting information; experimental part
p. 2392 - 2396
(2011/11/05)
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- Direct synthesis of water-tolerant alkyl indium reagents and their application in palladium-catalyzed couplings with aryl halides
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A direct result: Alkyl indium reagents are synthesized by the insertion of indium into alkyl halide mediated by CuCl. The synthetic utility of these reagents is demonstrated by their palladium-catalyzed coupling with aryl halides (see scheme). The reagents are compatible with various functional groups, and this makes the protocol generally useful in organic synthesis. DMA=N,N-dimethylacetamide, TBS=tert-butyldimethylsilyl.
- Shen, Zhi-Liang,Goh, Kelvin Kau Kiat,Yang, Yong-Sheng,Lai, Yin-Chang,Wong, Colin Hong An,Cheong, Hao-Lun,Loh, Teck-Peng
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supporting information; experimental part
p. 511 - 514
(2011/03/17)
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- Efficient heterogeneously palladium-catalysed synthesis of stilbenes and bibenzyls
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An alternative heterogeneously palladium catalysed procedure for the synthesis of functional stilbenes and bibenzyls is reported. Starting from aryl bromides and using simple commercially available Pd/C catalyst at a low catalytic rate (1 mol%), stilbenes are obtained with 30-100% GC-yields and bibenzyls are produced in a one-pot fashion with 27-100% GC-yields. The procedure showed, however, some limitations when applied to strongly deactivated aryl bromides that could be in some extent overcome by using corresponding iodo derivatives.
- Cusati, Giuseppe,Wedig, Anja,Djakovitch, Laurent
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scheme or table
p. 77 - 81
(2010/04/23)
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- Cross-coupling reactions of primary alkylboronic acids with aryl triflates and aryl halides
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The cross-coupling reactions of primary alkylboronic acids with aryl triflates and aryl halides has been successfully achieved using PdCl2(dppf)·CH2Cl2 in the presence of potassium carbonate to provide the corresponding Su
- Molander, Gary A.,Yun, Chang-Soo
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p. 1465 - 1470
(2007/10/03)
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- Aryl Radicals from Electrochemical Reduction of Aryl Halides. Addition on Olefins
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Aryl radicals generated by direct and indirect (by means of an aromatic anion radical mediator) electrochemistry are reacted with olefins in liquid ammonia and in organic solvents (Me2SO, MeCN, DMF).The arylated product is obtained in good yield in the latter case.In pure liquid NH3, the yields are extremely poor.They are improved upon addition of a proton donor such as urea or water; further increase of yields is obtained upon addition of 2-propanol.A reaction mechanism is proposed based on these observations and on the results of deuterium incorporation experiments.Cyclic voltammetry is used to determine the rate constant of the key step in the mechanism, viz, the addition of the aryl radical to the olefin, through its competition with its reaction with nucleophiles in the framework of an SRN1 substitution process.
- Chami, Zoubida,Gareil, Monique,Pinson, Jean,Saveant, Jean-Michel,Thiebault, Andre
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p. 586 - 595
(2007/10/02)
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- EFFECTIVE HYDROGENATION OF CARBON-CARBON TRIPLE BONDS BY NaBH4/PdCl2 IN POLYETHYLENE GLYCOL/CH2Cl2: USEFULNESS OF PEG IN SYNTHETIC REACTIONS
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The NaBH4-PdCl2-polyethylene glycol-CH2Cl2 system has been found to be effective for the hydrogenation of carbon-carbon triple bonds to the corresponding cis-alkenes.
- Suzuki, N.,Kaneko, Y.,Tsukanaka, T.,Nomoto, T.,Ayaguchi, Y.,Izawa, Y.
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p. 2387 - 2392
(2007/10/02)
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- Redox-Photosensitized Reactions. 11. Ru(bpy)32+-Photosensitized Reactions of 1-Benzyl-1,4-dihydronicotinamide with Aryl-Substituted Enones, Derivatives of Methyl Cinnamate, and Substituted Cinnamonitriles: Electron-Transfer Mechanism and Structure-Reactivity Relationship
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Reactions of 1-benzyl-1,4-dihydronicotinamide (BNAH) with aryl-substituted enones and derivatives of methyl cinnamate and cinnamonitrile (1a-u) are photosensitized by Ru(bpy)32+ (bpy = 2,2'-bipyridine).The reduction of carbon-carbon double bonds commonly requires the substitution of either an electron-withdrawing aryl group or two phenyl groups at the β-carbon atom of 1.With enones which possess one aryl substituent with no extra electron-withdrawing group at the β position, the photosensitized reactions result in no two-electron reductions but give 1:1 adducts (4d-h) along with half-reduced dimers of olefins (3d and 3g) and a half-oxidized dimer of BNAH (5).The observed results can be easily interpreted by assuming the intervention of 1-benzyl-3-carbamoyl-1,4-dihydropyridin-4-yl radical (BNA.) and half-reduced species (.1-H) as key intermediates that are formed by mediated electron-proton transfer from BNAH to 1 in which Ru(bpy)32+ acts as a one-electron shuttle upon photoexcitation in the initial electron transfer.Whether BNA. undergoes electron transfer to or a radical-coupling reaction with .1-H depends on steric and electronic properties of .1-H which should be affected by the substituents at the radical center.Mechanistic implications for thermal reactions of NADH models with olefins in the dark are briefly discussed on the basis of these observations.
- Pac, Chyongjin,Miyauchi, Yoji,Ishitani, Osamu,Ihama, Mikio,Yasuda, Masahide,Sakurai, Hiroshi
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- Chemistry of the tert-Butyl Radical: Polar Character, ρ Value for Reaction with Toluenes, and the Effect of Radical Polarity on the Ration of Benzylic Hydrogen Abstraction to Addition to Aromatic Rings
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We have reexamined the reactions of tert-butyl radicals with toluenes and have obtained a ρ value of 0.49 +/- 0.04 at 80 deg C.The new, independent system involves the quantification of all of the principal products from the reaction of tert-butyl radicals with mixtures of toluene and substituted toluene.Five major products contain benzyl fragments and are formed in significant yields: two symmetrical bibenzyls, the cross bibenzyl, and the two neopentylbenzenes that result from combination of tert-butyl and the two benzyl radicals.Attack on the side chain is a major reaction of free tert-butyl radicals and is the only significant reaction that they undergo other than cage and termination reactions. tert-Butyl radicals do not add to the ring of toluenes.Data on the relative rates of addition to benzenes and hydrogen abstraction from toluenes are collected for a series of radicals including hydrogen atoms; methyl, isopropyl, and tert-butyl radicals; and p-nitrophenyl, p-bromophenyl, and phenyl radicals.The data demonstrate that more electrophilic radicals have a larger tendency to add to rings whereas more nucleophilic radicals have a larger tendency to abstract benzylic hydrogens.
- Pryor, William A.,Tang, Felicia Y.,Tang, Robert H.,Church, Daniel F.
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p. 2885 - 2891
(2007/10/02)
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