- The Enantioselective Copolymerisation of Allylbenzene, 1-Allyl-4-(trifluoromethyl)benzene, and 1-Allyl-4-methoxybenzene with Carbon Monoxide
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The olefins mentioned in the title were copolymerized with CO in the presence of palladium catalysts modified with dicyclohexyl {(R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyl}phosphine. Productivities up to 95 g/(g Pd · h) were achieved. The obtained c
- Di Benedetto, Silvia,Consiglio, Giambattista
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- Quantitative Analysis on Two-Point Ligand Modulation of Iridium Catalysts for Chemodivergent C-H Amidation
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The transition-metal-catalyzed nitrenoid transfer reaction is one of the most attractive methods for installing a new C-N bond into diverse reactive units. While numerous selective aminations are known, understanding complex structural effects of the key intermediates on the observed chemoselectivity is still elusive in most cases. Herein, we report a designing approach to enable selective nitrenoid transfer leading to sp2 spirocyclization and sp3 C-H insertion by cooperative two-point modulation of ligands in the CpXIr(III)(κ2-chelate) catalyst system. Computational analysis led us to interrogate structural motifs that can be attributed to the desired mechanistic dichotomy. Multivariate linear regression analysis on the perturbation on the η5-cyclopentadienyl ancillary (CpX) and LX coligand, wherein we prepared over than 40 new catalysts for screening, allowed for construction of an intuitive yet robust statistical model that predicts a large set of chemoselective outcomes, implying that the catalysts' structural effects play a critical role on the chemoselective nitrenoid transfer. On the basis of this quantitative analysis, a new catalytic platform is now established for the unique lactam formation, leading to the unprecedented chemoselective reactivity (up to >20:1) toward a diverse array of competing sites, such as tertiary, secondary, benzylic, allylic C-H bonds, and aromatic πsystem.
- Hwang, Yeongyu,Jung, Hoimin,Lee, Euijae,Kim, Dongwook,Chang, Sukbok
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supporting information
p. 8880 - 8889
(2020/12/23)
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- Manganese catalyzed dehydrogenative silylation of alkenes: Direct access to allylsilanes
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Dehydrogenative silylation of alkenes with silanes to produce allylsilanes is achieved through manganese catalysis with a wide scope of substrate tolerance. This transformation involves silane radicals initiated by manganese complex without additional oxidant additives. It offers a general, convenient and practical protocol with excellent functional group compatibility and gram-scale capacity for the modular synthesis of allylsilanes.
- Wu, Shang,Zhang, Ying,Jiang, Hongyan,Ding, Ning,Wang, Yanbin,Su, Qiong,Zhang, Hong,Wu, Lan,Yang, Quanlu
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supporting information
(2020/06/03)
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- Photo-Ni-Dual-Catalytic C(sp2)-C(sp3) Cross-Coupling Reactions with Mesoporous Graphitic Carbon Nitride as a Heterogeneous Organic Semiconductor Photocatalyst
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The synergistic combination of a heterogeneous organic semiconductor mesoporous graphitic carbon nitride (mpg-CN) and a homogeneous nickel catalyst with visible-light irradiation at room temperature affords the C(sp2)-C(sp3) cross-co
- Antonietti, Markus,Ghosh, Indrajit,K?nig, Burkhard,Khamrai, Jagadish,Savateev, Aleksandr
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p. 3526 - 3532
(2020/04/09)
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- Palladium-Catalyzed Oxidative Allylation of Sulfoxonium Ylides: Regioselective Synthesis of Conjugated Dienones
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The first examples of palladium-catalyzed allylic C-H oxidative allylation of sulfoxonium ylides to afford the corresponding conjugated dienones with moderate to good yields have been established. The features of this novel conversion include mild reaction conditions, wide substrate scope, and excellent regioselectivity.
- Li, Chunsheng,Li, Meng,Zhong, Wentao,Jin, Yangbin,Li, Jianxiao,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 872 - 875
(2019/05/16)
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- Palladium-catalyzed oxidative allylation of bis[(pinacolato)boryl]methane: Synthesis of homoallylic boronic esters
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A palladium-catalyzed oxidative allylation of bis[(pinacolato)boryl]methane to afford the corresponding homoallylic organoboronic esters with moderate to excellent yields is reported. This novel transformation provides an efficient strategy for the construction of homoallylic organoboronic esters in one step with a broad substrate scope. It is proposed that the palladium-catalyzed oxidative allylic C-H bond activation process may be involved in the catalytic cycle.
- Li, Chunsheng,Li, Meng,Li, Jianxiao,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 66 - 69
(2017/12/27)
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- Anti-Markovnikov rearrangement in sulfur mediated allylic C-H amination of olefins
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Cationic rearrangement reactions usually follow Markovnikov's rule to give more substituted carbocations as stable intermediates. During our study on sulfur mediated allylic C-H amination of olefins, very rare cases of anti-Markovnikov rearrangement from secondary carbocations toward primary carbocations or primary triflates were observed.
- Zhang, Zhong,Du, Hongguang,Xu, Jiaxi,Li, Pingfan
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supporting information
p. 11547 - 11550
(2016/10/03)
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- Palladium-catalyzed aerobic oxidative double allylic C-H oxygenation of alkenes: A novel and straightforward route to α,β-unsaturated esters
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A mild tandem oxidative functionalization of allyl aromatic hydrocarbons was accomplished using the catalytic system of Pd(OAc)2/DMA under 1 atm O2. The green twofold C-O bond formation involving double allylic C-H oxygenation unlocks opportunities for markedly different synthetic strategies. Moreover, the reaction affords aryl α,β-unsaturated esters directly from readily available terminal olefins in moderate to good yields with excellent chemo- and stereoselectivities.
- Yang, Wanfei,Chen, Huoji,Li, Jianxiao,Li, Chunsheng,Wu, Wanqing,Jiang, Huanfeng
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p. 9575 - 9578
(2015/06/08)
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- Palladium-catalyzed aerobic oxidative allylic C-H arylation of alkenes with polyfluorobenzenes
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An aerobic oxidative cross-coupling reaction of alkenes with polyfluorobenzenes, through palladium-catalyzed allylic C-H activation, is reported. This attractive route provides a new way to forge allylic C-C bonds of valuable products, in good yields, with high regioselectivity.
- Jiang, Huanfeng,Yang, Wanfei,Chen, Huoji,Li, Jianxiao,Wu, Wanqing
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supporting information
p. 7202 - 7204
(2014/07/07)
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- Method for Allylating and Vinylating Aryl, Heteroaryl, Alkyl, and Alkene Halogenides Using Transition Metal Catalysis
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What is described is a process for preparing organic compounds of the general formula (I) R—R′??(I) by converting a corresponding compound of the general formula (II) R—X ??(II) in which X is fluorine, chlorine, bromine or iodine to an organomagnesium compound of the general formula (III) [M+]n[RmMgXkY1]??(III) wherein compounds of the formula (III) are reacted with a compound of the general formula (IV) characterized in that the reaction of (III) with (IV) is performed in the presence of a) catalytic amounts of an iron compound, based on the compound of the general formula (II), and optionally in the presence of b) a nitrogen-, oxygen- and/or phosphorus-containing additive in a catalytic or stoichiometric amount, based on the compound of the general formula (II).
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Paragraph 0062; 0063; 0064
(2013/07/25)
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- Highly regioselective palladium-catalysed oxidative allylic C-H carbonylation of alkenes
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Pd-catalysed direct oxidative carbonylation of allylic C-H bonds with carbon monoxide was first described. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalysed allylic carbonylation can be lifted, which provides a new route for accessing more synthetically useful β-enoic acid esters with high regioselectivity. The Royal Society of Chemistry 2011.
- Chen, Huoji,Cai, Congbi,Liu, Xiaohang,Li, Xianwei,Jiang, Huanfeng
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supporting information; scheme or table
p. 12224 - 12226
(2011/12/14)
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- Practical iron-catalyzed allylations of aryl grignard reagents
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An operationally simple iron-catalyzed reductive cross-coupling reaction between aryl halides and allyl electrophiles has been developed. The underlying domino process exhibits high versatility with respect to the allylic leaving group (acetate, tosylate, diethyl phosphate, methyl carbonate, trimethylsilanolate, methanethiolate, chloride, bromide) and high economic and environmental sustainability with respect to the catalyst system (0.2-5 mol% tris(acetylacetonato)iron(III), ligand-free) and reaction conditions (tetrahydrofuran, 0°C, 45 min).
- Mayer, Matthias,Czaplik, Waldemar M.,Von Wangelin, Axel Jacobi
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supporting information; experimental part
p. 2147 - 2152
(2010/12/18)
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- Stannylated polynorbornenes as new reagents for a clean stille reaction
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New functionalized polynorbornenes have been obtained in good yields by vinylic copolymerization of norbornene with a (norbornenyl)Sn-Bu2Cl monomer, catalyzed by [Ni(C6F5)2(SbPh 3)2]. Subsequent functionalization produces a wide variety of polymers with different -SnBu2R groups (R = aryl, vinyl, alkynyl). The polymers can be used as R-transfer reagents in Stille couplings, thereby providing easy workup and separation of the polymeric tin byproducts from the coupling products. Tin contents of around 0.05 wt% are found in the Stille products. The stannylated polymers can be recycled and reused with good efficiency.
- Carrera, Nora,Gutierrez, Enrique,Benavente, Rut,Villavieja, M. Mar,Albeniz, Ana C.,Espinet, Pablo
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scheme or table
p. 10141 - 10148
(2009/11/30)
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- The mechanism for the rhodium-catalyzed decarbonylation of aldehydes: A combined experimental and theoretical study
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The mechanism for the rhodium-catalyzed decarbonylation of aldehydes was investigated by experimental techniques (Hammett studies and kinetic isotope effects) and extended by a computational study (DFT calculations). For both benzaldehyde and phenyl acetaldehyde derivatives, linear Hammett plots were obtained with positive slopes of +0.79 and +0.43, respectively, which indicate a buildup of negative charge in the selectivity-determining step. The kinetic isotope effects were similar for these substrates (1.73 and 1.77 for benzaldehyde and phenyl acetaldehyde, respectively), indicating that similar mechanisms are operating. A DFT (B3LYP) study of the catalytic cycle indicated a rapid oxidative addition into the C(O)-H bond followed by a rate-limiting extrusion of CO and reductive elimination. The theoretical kinetic isotope effects based on this mechanism were in excellent agreement with the experimental values for both substrates, but only when migratory extrusion of CO was selected as the rate-determining step.
- Fristrup, Peter,Kreis, Michael,Palmelund, Anders,Norrby, Per-Ola,Madsen, Robert
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p. 5206 - 5215
(2008/12/22)
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- Inter- and intramolecular palladium-catalyzed allyl cross-coupling reactions using allylindium generated in situ from allyl acetates, indium, and indium trichloride
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Inter- and intramolecular palladium-catalyzed ally! cross-coupling reactions using allylindium generated in situ by treatment of allyl acetates with indium and indium trichloride in the presence of Pd0 catalyst and nBuNMe2 in DMF were successfully demonstrated. Allylindium species generated in situ by reductive transmetalation of π- allylpalladium(II) complexes, obtained from a variety of allyl acetales in the presence of Pd0 catalyst together with indium and indium trichloride, were found to be capable of acting as effective nucleophilic coupling partners in Pd-catalyzed cross-coupling reactions. A variety of allyl acetates such as but-l-en-3-yl acetate, crotyl acetate, and 2-methylallyl acetate afforded the corresponding allylic compounds in good yields in cross-coupling reactions. Various electrophilic cross-coupling partners such as aryl iodides and vinyl bromides and triflates participate in these reactions. Not only intermolecular but also intramolecular Pd-catalyzed cross-coupling reactions work equally well to produce the desired allylic coupling products in good yields.
- Seomoon, Dong,Lee, Kooyeon,Kim, Hyunseok,Lee, Phil Ho
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p. 5197 - 5206
(2008/02/10)
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- Palladium-indium-indium(III) chloride-mediated allyl cross-coupling reactions using allyl acetates
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Allylindiums in situ generated by reductive transmetalation of π-allylpalladium(II) complexes, obtained from allyl acetates and palladium(0) catalyst, with indium and indium(III) chloride are effective nucleophilic cross-coupling partners in Pd-catalyzed allyl cross-coupling reactions with a variety of electrophilic cross-coupling partners.
- Lee, Phil Ho,Seomoon, Dong,Lee, Kooyeon,Kim, Sundae,Kim, Hyunseok,Kim, Hyun,Shim, Eunkyong,Lee, Miae,Lee, Seokju,Kim, Misook,Sridhar, Madabhushi
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p. 1641 - 1645
(2007/10/03)
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- Process of heterocoupling by electrolytic microbattery, use of cobalt for implementing said coupling and composition for doing so
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This invention has as its object a process for preparation of vinyl aryl derivatives by an electrochemical path. This process is defined in that it consists in subjecting a composition that comprises a cobalt salt, an aromatic halide and a vinyl ester to the action of a metal that is at least as reducing as zinc. Application to organic synthesis.
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- A highly effective (Triphenyl phosphite)palladium catalyst for a cross-coupling reaction of allylic alcohols with organoboronic acids
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The cross coupling reaction of aryl and vinyl boronic acids and allylic alcohols proceeded smoothly in toluene or dioxane in the presence of a (triphenyl phosphite)palladium catalyst to give the corresponding allylbenzene derivatives and 1,4-dienes. Neither cocatalysts for promoting C-O bond cleavage of allylic alcohols nor bases for activation of organoboron reagents are required for promoting the coupling process. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- Kayaki, Yoshihito,Koda, Takashi,Ikariya, Takao
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p. 4989 - 4993
(2007/10/03)
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- New chemical cross-coupling between aryl halides and allylic acetates using a cobalt catalyst
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(Figure presented) The cobalt-catalyzed coupling reaction of aromatic halides and allylic acetates proceeds readily under mild conditions in the presence of the appropriate reducing agent to produce allylaromatic derivatives either in pure acetonitrile (aryl bromides) or in an acetonitrile/pyridine mixture (aryl chlorides).
- Gomes, Paulo,Gosmini, Corinne,Perichon, Jacques
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p. 1043 - 1045
(2007/10/03)
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- Cobalt-catalyzed direct electrochemical cross-coupling between aryl or heteroaryl halides and allylic acetates or carbonates
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The electroreduction of a mixture of functionalized aromatic or heteroaromatic bromides or chlorides and allylic compounds such as acetates or carbonates in an electrochemical cell fitted with a sacrificial iron anode affords, in the presence of cobalt halide associated with pyridine as ligand in acetonitrile or DMF, the corresponding coupling product in good yields.
- Gomes, Paulo,Gosmini, Corinne,Perichon, Jacques
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p. 1142 - 1145
(2007/10/03)
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- Cross-coupling reaction of organostannanes with aryl halides catalyzed by nickeltriphenylphosphine or nickel-lithium halide complex
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A nickel(0) complex used in combination with lithium bromide was found to enhance the rate of the cross-coupling reaction of aryl halides with organostannanes, whereas a Ni(0) catalyst combined with Ph3P was applicable to a wide variety of aryl halides including aryl chlorides.
- Shirakawa, Eiji,Yamasaki, Kenji,Hiyama, Tamejiro
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p. 1544 - 1549
(2007/10/03)
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- Nickel-catalyzed direct electrochemical cross-coupling between aryl halides and activated alkyl halides
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The electrochemical reduction of a mixture of aryl halides and activated alkyl halides in DMF in the presence of catalytic amount of NiBr2bipy leads to cross-coupling products in good to high yields. The method applies to the synthesis of α-aryl ketones, α-aryl esters, and allylated compounds from readily available organic halides. Optimization of the process has been obtained by slowly adding the most reactive organic halide (usually the activated alkyl halide) during the electrolysis which is best conducted at 70 °C when aryl bromides are involved.
- Durandetti, Muriel,Nedelec, Jean-Yves,Perichon, Jacques
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p. 1748 - 1755
(2007/10/03)
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- Electrochemical Conversion of Functionalised Aryl Chlorides and Bromides to Arylzinc Species
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Electroreduction of aromatic chlorides or bromides in a cell fitted with a sacrificial zinc anode, in the presence of a nickel 2,2'-bipyridine complex affords the corresponding organozinc species in good yield.
- Sibille, Soline,Ratovelomanana, Victorin,Perichon, Jacques
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p. 283 - 284
(2007/10/02)
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