- Copper-promoted difunctionalization of unactivated alkenes with silanes
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An efficient copper-catalyzed cascade difunctionalization of N-allyl anilines toward the synthesis of silylated indolines using commercially available silanes has been reported. This strategy provides a new avenue for the synthesis of a diverse array of i
- Chen, Xiaoyu,Guo, Zhuangzhuang,Li, Jingya,Wu, Yangjie,Wu, Yusheng,Xue, Yingying,Zou, Dapeng
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p. 989 - 994
(2022/02/11)
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- A Next-Generation Air-Stable Palladium(I) Dimer Enables Olefin Migration and Selective C?C Coupling in Air
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We report a new air-stable PdI dimer, [Pd(μ-I)(PCy2tBu)]2, which triggers E-selective olefin migration to enamides and styrene derivatives in the presence of multiple functional groups and with complete tolerance of air. The same dimer also triggers extremely rapid C?C coupling (alkylation and arylation) at room temperature in a modular and triply selective fashion of aromatic C?Br, C?OTf/OFs, and C?Cl bonds in poly(pseudo)halogenated arenes, displaying superior activity over previous PdI dimer generations for substrates that bear substituents ortho to C?OTf.
- Kundu, Gourab,Rissanen, Kari,Schoenebeck, Franziska,Sperger, Theresa
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supporting information
p. 21930 - 21934
(2020/10/02)
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- Nickel(0)-Catalyzed N-Allylation of Amides and p-Toluenesulfonamide with Allylic Alcohols under Neat and Neutral Conditions
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Nickel(0)-catalyzed direct N-allylation of amides and p-toluenesulfonamide with allylic alcohols took place in the presence of Ni0–diphosphine complexes. The corresponding N-allylated (and/or N,N-diallylated) products were obtained in moderate to high yields under neutral conditions.
- Azizi, Mohamed Salah,Edder, Youssef,Karim, Abdallah,Sauthier, Mathieu
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p. 3796 - 3803
(2016/08/16)
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- Generation and trapping of ketenes in flow
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Ketenes were generated by the thermolysis of alkoxyalkynes under flow conditions, and then trapped with amines and alcohols to cleanly give amides and esters. For a 10 min reaction time, temperatures of 180, 160, and 140 °C were required for >95% conversion of EtO, iPrO, and tBuO alkoxyalkynes, respectively. Variation of the temperature and flow rate with inline monitoring of the output by IR spectroscopy allowed the kinetic parameters for the conversion of 1-ethoxy-1-octyne to be easily estimated (Ea = 105.4 kJ/mol). Trapping of the in-situ-generated ketenes by alcohols to give esters required the addition of a tertiary amine catalyst to prevent competitive [2+2] addition of the ketene to the alkoxyalkyne precursor.
- Henry, Cyril,Bolien, David,Ibanescu, Bogdan,Bloodworth, Sally,Harrowven, David C.,Zhang, Xunli,Craven, Andy,Sneddon, Helen F.,Whitby, Richard J.
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p. 1491 - 1499
(2015/03/04)
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- Metal-free reductive cleavage of C-N and S-N bonds by photoactivated electron transfer from a neutral organic donor
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A photoactivated neutral organic super electron donor cleaves challenging arenesulfonamides derived from dialkylamines at room temperature. It also cleaves a)ArC-NR and b)ArN-C bonds. This study also highlights the assistance given to these cleavage reactions by the groups attached to N in (a) and to C in (b), by lowering LUMO energies and by stabilizing the products of fragmentation. Radical fragmentations: Electron transfer from the photoactivated neutral electron donor 1 delivers high yields of S-N and C-N cleavage products for a range of nitrogen-containing species. These reactions proceed at room temperature and under mild reaction conditions in the absence of any metal reagents. DMF=N,N-dimethylformamide, Ts=4-toluenesulfonyl.
- O'Sullivan, Steven,Doni, Eswararao,Tuttle, Tell,Murphy, John A.
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supporting information
p. 474 - 478
(2014/01/23)
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- Visible-light-induced photocatalytic reductive transformations of organohalides
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A photo opportunity: A visible-light-excited iridium catalyst delivers electrons from an amine to an organohalide. The electron transfer then induces reductive scission of the carbon-halogen bond, generating the corresponding alkyl, alkenyl, and aryl radical that can undergo cyclization and hydrodehalogenation reactions. Copyright
- Kim, Hyejin,Lee, Chulbom
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p. 12303 - 12306
(2013/02/23)
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- Highly efficient and regioselective allylic amination of allylic alcohols catalyzed by [Mo3PdS4] cluster
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A highly efficient and regioselective allylation reaction of amines with allylic alcohols under mild conditions catalyzed by the cubane-type sulfido cluster [(Cp*Mo)3S4Pd(dba)][PF6] with H3BO3 as an additive has been developed. A variety of amines and allylic alcohols are investigated, and in the case of allylic alcohols bearing substituents at either α- or γ-position only linear allylic amination products are obtained.
- Tao, Yinsong,Zhou, Yuhan,Qu, Jingping,Hidai, Masanobu
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experimental part
p. 1982 - 1984
(2010/06/21)
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- Highly efficient and regioselective allylation with allylic alcohols catalyzed by [Mo3S4Pd(η3-allyl)] clusters
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(Figure presented) A highly efficient and regioselective allylation reaction of amines and active methylene compounds directly using allylic alcohols under mild conditions catalyzed by the novel cubane-type sulfido [(CpMo)3(μ3-S)4Pd(η3-allyl)] [PF6]2 clusters has been developed. A variety of allylic alcohols and nucleophiles including amines and active methylene compounds are investigated, and in the case of allylic alcohols bearing substituents at either the α- or γ-position only linear products are obtained.
- Tao, Yinsong,Wang, Bo,Wang, Baomin,Qu, Lihong,Qu, Jingping
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experimental part
p. 2726 - 2729
(2010/08/06)
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- Synthesis of heterocyclic compounds by ring-closing metathesis (RCM): Preparation of oxygenated or nitrogenated compounds
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Novel methods for heterocyclic synthesis by metathesis have been developed. Versatile heterocyclic compounds were easily prepared in good yield from intermediate olefins by ring-closing olefin metathesis using the catalyst dichloro(benzylidene)bis(tricycl
- Sanchez, Isabel,Pujol, Maria Dolors
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p. 1823 - 1828
(2007/10/03)
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- Highly selective synthesis of (E)-N-aryl-N-(1-propenyl) ethanamides via isomerization of N-allyl ethanamides catalyzed by ruthenium complexes
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A convenient and highly selective method of synthesis of (E)-N-aryl-N-(1-propenyl)ethanamides via isomerization of respective N-allyl-N-arylethanamides catalyzed by [RuClH(CO)(PPh3)3] has been described. N-Allyl-N-arylethanamides hav
- Krompiec, Stanislaw,Pigulla, Mariola,Szczepankiewicz, Wojciech,Bieg, Tadeusz,Kuznik, Nikodem,Leszczynska-Sejda, Katarzyna,Kubicki, Maciej,Borowiak, Teresa
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p. 7095 - 7098
(2007/10/03)
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- Formation of N-acetyl-2,3-dihydroindoles by the electrochemical cleavage of the carbon-chlorine bond in N-allyl-2-chloroacetanilides
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The electrochemically induced radical cyclization of N-allyl-2-chloroacetanilides to form N-acetyl-2,3-dihydroindoles has been demonstrated where the phenyl ring contains an electron withdrawing substituent such as cyano. Cyclization of N-allyl-2-chloroacetanilide was successful in the presence of (E)-stilbene as electron transfer agent yielding 1-acetyl-3-methyl-2,3-dihydroindole. Indirect electrochemical reduction of N-cinnamyl-2-chloroacetanilide leads mainly to cleavage of the cinnamyl group and only a low yield of N-acetyl-3-benzyl-2,3-dihydroindole was obtained. Acta Chemica Scandinavica 1998.
- Dias, Marylene,Gibson, Mandy,Grimshaw, James,Hill, Ian,Trocha-Grimshaw, Jadwiga,Hammerich, Ole
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p. 549 - 554
(2007/10/03)
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- Synthesis of Five-membered Lactams by α-Carbamoyl Radical Cyclisations
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Free-radical cyclisation of N-allyl-α-carbamoyl radicals generated by tributyltin radical-mediated cleavage of carbon-chlorine or carbon-sulphur bonds has been studied in some detail.The radicals substituted at the α position by methylthio (phenylthio), c
- Sato, Tatsunori,Wada, Yasuko,Nishimoto, Mami,Ishibashi, Hiroyuki,Ikeda, Masazumi
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p. 879 - 886
(2007/10/02)
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- Homogeneous Catalysis. Transition-Metal-Catalyzed Claisen Rearrangements
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Palladium(0), palladium(II), rhodium(I), and iridium(I) complexes catalyze the rearrangement of allyl imidates to allyl amides under mild conditions.The palladium(II) catalysis is characterized by exclusive regioselectivity and high steroeselectivity whereas the palladium(0), rhodium(I), and iridium(I) catalysts generally give both the and rearrangement products and although the palladium(0) catalyst can give high stereoselectivity, the rhodium(I) and iridium(I) catalysts are nonstereoselective.After a series of experiments using chiral substrates and substrates with specific deuterium labels, the mechanisms of these catalytic reactions have been elucidated.The palladium(II) catalysis is proposed to proceed via cyclic carbonium ion intermediates, and the mechanism resembles the thermal uncatalyzed Claisen rearrangement path.The palladium(0) catalysis is a form of catalytic allylation involving oxidative addition followed by nucleophilic attack on a ?-allyl intermediate.The mechansim of the rhodium(I) and iridium(I) catalysis was not as fully investigated as the others, but it appears to involve carbonium ion intermediates formed by cleavage of the allyl-oxygen bond.
- Schenck, Terry G.,Bosnich, B.
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p. 2058 - 2066
(2007/10/02)
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- Direct N-Allylation of Amides with 2-Allylisourea Catalyzed by Palladium(0)
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Direct N-allylation of amides catalyzed by palladium(0) complexes took place under neutral conditions by the use of 2-allylisourea as the allylating agent.
- Inoue, Yoshio,Taguchi, Masaaki,Hashimoto, Harukichi
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p. 2721 - 2722
(2007/10/02)
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