- One-pot Construction of Difluorinated Pyrrolizidine and Indolizidine Scaffolds via Copper-Catalyzed Radical Cascade Annulation
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A convenient approach to the synthesis of diverse difluorinated nitrogen-containing polycycles via a copper-catalyzed radical cascade annulation of amine-containing olefins and ethyl bromodifluoroacetate was developed. Three new bonds, including a Csp3 ?CF2 and two C?N bonds, are forged simultaneously in this strategy. Through this strategy, a series of difluorinated pyrrolizidine and indolizidine derivatives have been conveniently synthesized in good yields. (Figure presented.).
- Wang, Xiaoyang,Li, Miao,Yang, Yanyan,Guo, Minjie,Tang, Xiangyang,Wang, Guangwei
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- Platinum(II)-Crosslinked Single-Chain Nanoparticles: An Approach towards Recyclable Homogeneous Catalysts
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We introduce the synthesis and in-depth characterization of platinum(II)-crosslinked single-chain nanoparticles (PtII-SCNPs) to demonstrate their application as a recyclable homogeneous catalyst. Specifically, a linear precursor copolymer of styrene and 4-(diphenylphosphino)styrene was synthesized via nitroxide-mediated polymerization. The triarylphosphine ligand moieties along the backbone allowed for the intramolecular crosslinking of single chains via the addition of [Pt(1,5-cyclooctadiene)Cl2] in dilute solution. The successful formation of well-defined PtII-SCNPs was evidenced by size exclusion chromatography, dynamic light scattering, nuclear magnetic resonance (1H, 31P{1H}, 195Pt), and diffusion-ordered spectroscopy. Finally, the activity of the PtII-SCNPs as homogeneous, yet recyclable catalyst was successfully demonstrated using the example of the amination of allyl alcohol.
- Kn?fel, Nicolai D.,Rothfuss, Hannah,Willenbacher, Johannes,Barner-Kowollik, Christopher,Roesky, Peter W.
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- Rate acceleration and diastereoselectivity in chelation-controlled indium-promoted Barbier allylation of pyridine-2- and quinoline-2-imines in aqueous solvents
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The imines generated in situ from 2-pyridinecarboxaldehyde/2- quinolinecarboxaldehyde and aryl amines undergo indium-mediated Barbier allylation in aqueous media to provide homoallylic amines. Crotyl and cinnamyl bromides lead to diastereoselective allyla
- Kumar, Subodh,Kaur, Pervinder
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- Thioamination of Alkenes with Hypervalent Iodine Reagents
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An efficient thioamination of alkenes mediated by iodine(III) reagents is described. The use of different sulfur nucleophiles allows the flexible synthesis of 1,2-aminothiols from alkenes. By employing chiral iodine(III) reagents, a stereoselective version of the thioamination protocol has also been developed.
- Mizar, Pushpak,Niebuhr, Rebecca,Hutchings, Matthew,Farooq, Umar,Wirth, Thomas
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- Indium-mediated barbier reactions of azides: A facile synthesis of N-allylamine derivatives
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N-Allylic amines are conveniently prepared in high yields by the reaction of azides with allylindium reagents in the presence of sodium iodide in DMF at ambient temperature.
- Yadav,Madhuri,Reddy,Reddy, G. S. Kiran Kumar,Sabitha
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Read Online
- Nickel-Catalyzed Aminofluoroalkylation of Alkenes: Access to Difluoroalkylated N-Containing Heterocyclic Compounds
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A nickel-catalyzed aminofluoroalkylative cyclization of unactive alkenes with iododifluoromethyl ketones was developed to construct versatile difluoroalkylated Nitrogen-containing heterocycles including aziridines, pyrrolidines and piperidines in moderate to high yields. This method features a broad substrate scope and has been demonstrated on gram scale.
- Fu, Xiaoyi,Zhang, Tianyu,Wu, Jingjing,Sun, Yijie,Wu, Fanhong
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supporting information
(2021/12/03)
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- Copper-Catalyzed Allylation of Amines with Cyclopropyldiphenylsulfonium Trifluoromethanesulfonate
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Cyclopropyldiphenylsulfonium salt, a famous ylide precursor previously extensively employed in the preparation of cyclic compounds, has been successfully utilized as an efficient allylation reagent in this work. The copper-catalyzed reactions of cyclopropyldiphenylsulfonium trifluoromethanesulfonate with amines in the presence of an appropriate ligand provided the N-allylated products in good yields. Aliphatic/ aromatic amines and primary/secondary amines were all converted under mild reaction conditions. This protocol was also applicable to N-functionalization of drug molecules, supplying the corresponding N-allylated compounds in satisfactory yields. The reaction, which showed good functional group tolerance with a wide range of substrates and excellent chemoselectivity, offers an interesting method for the synthesis of N-allyl amines.
- Ma, Yu,Tian, Ze-Yu,Zhang, Cheng-Pan,Zheng, Shuang-Yang
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supporting information
(2022/03/15)
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- Fused ring compound and preparation method thereof
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The invention provides a fused ring compound and a preparation method thereof. In the method, precursor compounds A and B prepared under the conditions of triethylamine as a base, DMF as a solvent andpalladium acetate and triphenylphosphine as a catalyst react to generate a series of new fused ring compounds with a unique stereoselectivity. Compared with the conventional fused ring compound, thefused ring compound prepared by the invention has a more complicated structure, a mild reaction condition and a high reaction yield. The fused ring compound also shows a broader prospect of use in chemical production and clinical medicine.
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Paragraph 0079; 0083-0084
(2021/09/21)
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- Halogenated method of aromatic compound
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The invention belongs to the field of organic synthesis, and particularly relates to synthesis of aromatic halogens, in particular to arylamine. The invention discloses a synthesis method of a corresponding ortho-halogenated product from aromatic compounds such as carbazole and phenol. The method comprises the following steps: adding a metal sulfonate salt catalyst, aromatic amine, carbazole, phenol and other hydrogen - heteroatom-containing aromatic compound reaction substrates, a halogenation reagent and a reaction solvent at a specific reaction temperature. After the drying agent is dried, the yield of the reaction product and the nuclear magnetic characterization determining structure are determined by column chromatography. The reaction product yield is determined by gas chromatography. By adopting the method, under the cheap metal salt catalyst, a plurality of ortho-substituted brominated and chloro products can be obtained with moderate to excellent yield.
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Paragraph 0054-0057
(2021/11/10)
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- Synthesis of functionalized indoles via palladium-catalyzed cyclization of N-(2-allylphenyl) benzamide: A method for synthesis of indomethacin precursor
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We developed an efficient method for synthesis of substituted N-benzoylindole via Pd(II)-catalyzed C-H functionalization of substituted N-(2-allylphenyl)benzamide. The reaction showed a broad substrate scope (including N-acetyl and N-Ts substrates) and substituted indoles were obtained in good to excellent yields. The most distinctive feature of this method lies in the high selectivity for N-benzoylindole over benzoxazine, and this is the first example of Pd(II)-catalyzed synthesis of substituted N-benzoylindole. Notably, this new method was applied for the synthesis of key intermediate of indomethacin.
- Chang, Zhe,Dong, Zheng,Ma, Tong,Zhang, Yu,Zhao, Depeng,Zhao, Heng
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supporting information
(2020/03/19)
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- Synthesis of Benzofuran and Indole Derivatives Catalyzed by Palladium on Carbon
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Benzofurans and indoles are key moieties in many natural products and pharmaceuticals. Herein, we describe a cheap and easy-to-execute strategy for the synthesis of benzofurans and indoles, employing Pd/C as the promoter. A variety of substituted allyl-anilines and allyl-phenols were converted into the desired products in good to excellent yields. Recycling of Pd/C was possible up to five cycles, keeping similar levels of reactivity.
- Savvidou, Anatoli,IoannisTzaras, Dimitrios,Koutoulogenis, Giorgos S.,Theodorou, Alexis,Kokotos, Christoforos G.
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supporting information
p. 3890 - 3897
(2019/06/27)
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- Indole compound and synthesizing and application methods thereof
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The invention relates to an indole compound and synthesizing and application methods thereof. The indole compound is prepared by selecting specific substituent groups. Experiments find that the indolecompound can achieve good inhibiting effects on prostatic cancer, good in drug-resistance-proofness and low in side effects when applied as an anti-cancer drug; besides, the synthesizing method of the indole compound comprises subjecting a compound with the structure shown as the formula (II), palladium acetate, benzoquinones and organic acids to reaction in solvent to obtain the indole compoundwith the structure shown as the formula (I). Experiment results show that the synthesizing method of the indole compound is low in requirements on substrate and high in product yield.
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Paragraph 0076-0079; 0093-0094; 0110-0111
(2019/10/22)
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- Palladium-Catalyzed Fluoroalkylative Cyclization of Olefins
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A palladium-catalyzed fluoroalkylative cyclization of olefins with readily available Rf-I reagents to afford the corresponding fluoroalkylated 2,3-dihydrobenzofuran and indolin derivatives with moderate to excellent yields is reported. This novel procedure provides an efficient method for the construction of Csp3-CF2 and C-O/N bonds in one step. A wide range of functional groups are tolerated. It is proposed that a radical/SET (single electron transfer) pathway proceeding via the fluoroalkyl radical may be involved in the catalytic cycle.
- Liao, Jianhua,Fan, Lianfeng,Guo, Wei,Zhang, Zhenming,Li, Jiawei,Zhu, Chuanle,Ren, Yanwei,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 1008 - 1011
(2017/03/15)
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- Green Organocatalytic Synthesis of Indolines and Pyrrolidines from Alkenes
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Employing a green and efficient 2,2,2-trifluoroacetophenone-catalyzed oxidation of alkenes, which utilizes H2O2 as the green oxidant, a novel and sustainable synthesis of indolines and pyrrolidines was developed. This constitutes a cheap, general and environmentally-friendly protocol for the synthesis of substituted nitrogen-containing heterocycles. A variety of substitution patterns, both aromatic and aliphatic moieties, are well tolerated leading to the desired nitrogen heterocycles in good to excellent yields. (Figure presented.).
- Theodorou, Alexis,Kokotos, Christoforos G.
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supporting information
p. 1577 - 1581
(2017/05/05)
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- Palladium-Catalyzed Aerobic Intramolecular Aminoacetoxylation of Alkenes Enabled by Catalytic Nitrate
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A mild aerobic intramolecular aminoacetoxylation method for the synthesis of pyrrolidine and indoline derivatives was achieved using molecular oxygen as the oxidant. A catalytic NOx species acts as an electron transfer mediator to access a high-valent palladium intermediate as the presumed active oxidant.
- Li, Jiaming,Grubbs, Robert H.,Stoltz, Brian M.
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supporting information
p. 5449 - 5451
(2016/11/17)
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- Copper-catalyzed radical cascade cyclization for the synthesis of phosphorated indolines
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A novel and convenient approach to the synthesis of various phosphorated indolines via a copper-catalyzed radical cascade cyclization reaction has been developed. The reaction employs cheap copper as the catalyst and K2S2O8 as the oxidant under mild conditions. Various alkenes and P-radical precursors are compatible with this transformation. Preliminary mechanistic studies reveal that the addition of the P-radical may initiate the reaction, and then oxidative cyclization may be achieved to afford the desired product. This journal is
- Zhang, Hong-Yu,Mao, Liu-Liang,Yang, Bin,Yang, Shang-Dong
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supporting information
p. 4101 - 4104
(2015/03/30)
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- Synthesis of novel [3,1]-benzothiazepine and [3,1]-benzoxazepine derivatives with antitumoral activity
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A new method for the synthesis of [3,1]-benzothiazepines and [3,1]-benzoxazepines from the reaction of C-allylanilines and isothiocyanates or isocyanates without the need for the isolation of any intermediate is described. The compounds were obtained in good to moderate yields and some exhibited cytotoxic activity against tumor cell lines. This journal is the Partner Organisations 2014.
- Martinez, Walter R.,Militao, Gardenia C. G.,Da Silva, Teresinha G.,Silva, Ricardo O.,Menezes, Paulo H.
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p. 14715 - 14718
(2014/04/17)
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- Efficient copper-catalyzed direct intramolecular aminotrifluoromethylation of unactivated alkenes with diverse nitrogen-based nucleophiles
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A mild, convenient, and step-economical intramolecular aminotrifluoromethylation of unactivated alkenes with a variety of electronically distinct, nitrogen-based nucleophiles in the presence of a simple copper salt catalyst, in the absence of extra ligand
- Lin, Jin-Shun,Xiong, Ya-Ping,Ma, Can-Liang,Zhao, Li-Jiao,Tan, Bin,Liu, Xin-Yuan
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supporting information
p. 1332 - 1340
(2014/04/03)
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- Silica-functionalized CuI: An efficient and selective catalyst for N-benzylation, allylation, and alkylation of primary and secondary amines in water
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Silica-functionalized CuI has been reported as an efficient and selective catalyst for the selective mono-N- and N,N-dibenzylation, allylation, and alkylation of primary amines with benzylic, allylic, and alkyl halides using NaOH as base in aqueous medium. By changing the reaction temperature, mono- or di-benzylation, allylation, or alkylation could be achieved in good yield and selectivity. Secondary amines have also been benzylated, allylated, and alkylated under similar conditions. SiO2-CuI has been characterized by Fourier transform-infrared, atomic absorption spectrometry, thermalgravimetric analysis, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, and found to be highly selective and recyclable under the reaction conditions. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.] Copyright
- Shamim, Tahira,Kumar, Vineet,Paul, Satya
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p. 620 - 632
(2014/01/17)
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- Palladium-catalyzed selective aminoamidation and aminocyanation of alkenes using isonitrile as amide and cyanide sources
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A mild and efficient palladium-catalyzed intermolecular aminoamidation and aminocyanation reaction of alkenes with a broad substrate scope has been developed. This cyclization process provides a valuable synthetic tool for obtaining substituted indolines, tetrahydroisoquinolines and pyrrolidines in good to excellent yields. This journal is
- Jiang, Huanfeng,Gao, Hanling,Liu, Bifu,Wu, Wanqing
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supporting information
p. 15348 - 15351
(2015/01/08)
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- Organocatalytic Stereoselective Iodoamination of Alkenes
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A new chiral thiohydantoin catalyst is used for the stereoselective iodoamination of alkenes. N-iodosuccinimide as the source of the electrophilic iodine is activated by catalytic amounts of different additives which also influence the regioselectivity of some cyclizations.
- Mizar, Pushpak,Burrelli, Alessandra,Günther, Erika,S?ftje, Martin,Farooq, Umar,Wirth, Thomas
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supporting information
p. 13113 - 13116
(2016/02/19)
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- Synthesis of quinolines and fused pyridocoumarins from N-propargylanilines or propargylaminocoumarins by catalysis with gold nanoparticles supported on TiO2
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[5,6]-Fused pyridocoumarins are prepared under mild conditions in excellent yields through the activation of the triple bond of 6-propargylaminocoumarins by gold nanoparticles supported on TiO2. The analogous reaction of N-propargylanilines with Au/TiO2 or Au/Al2O3 resulted in the formation of quinolines.
- Symeonidis, Theodoros S.,Lykakis, Ioannis N.,Litinas, Konstantinos E.
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p. 4612 - 4616
(2013/06/26)
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- A new entry to the phenanthridine ring system
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A new synthesis of phenanthridine derivatives having three-point diversity has been developed based on the sequential application of three-atom economic processes viz. aza-Claisen rearrangement, ring-closing enyne metathesis and Diels-Alder reaction as key steps. An unexpected isomerisation was observed during aza-Claisen rearrangement of N-allylanilines which may open up new opportunities in heterocyclic synthesis.
- Mondal, Poulomi,Thander, Latibuddin,Chattopadhyay, Shital K.
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supporting information; scheme or table
p. 1328 - 1331
(2012/04/04)
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- Copper-catalyzed enantioselective intramolecular alkene amination/intermolecular heck-type coupling cascade
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Enantioselective copper-catalyzed cyclization of γ- alkenylsulfonamides and a δ-alkenylsulfonamide in the presence of a range of vinyl arenes results in variously functionalized 2-substituted chiral nitrogen heterocycles via a formal alkene C-H functionalization process. Application of this reaction to the concise synthesis of a 5-HT7 receptor antagonist is demonstrated.
- Liwosz, Timothy W.,Chemler, Sherry R.
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supporting information; scheme or table
p. 2020 - 2023
(2012/03/12)
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- Catalytic enantioselective alkene aminohalogenation/cyclization involving atom transfer
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Problem solved: The title reaction was used for the synthesis of chiral 2-bromo, chloro, and iodomethyl indolines and 2-iodomethyl pyrrolidines (see scheme). Stereocenter formation is believed to occur by enantioselective cis aminocupration and C-X bond formation is believed to occur by atom transfer. The ultility of the products as versatile synthetic intermediates was demonstrated, as was a radical cascade cyclization sequence. Copyright
- Bovino, Michael T.,Chemler, Sherry R.
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supporting information; scheme or table
p. 3923 - 3927
(2012/05/20)
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- Assisted tandem catalytic RCM-aromatization in the synthesis of pyrroles and furans
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An assisted tandem catalytic transformation of diallyl amines and diallyl ethers into N-aryl pyrroles and furans, respectively, is described. The sequence relies on ring closing metathesis followed by dehydrogenation of the initially formed dihydropyrroles and dihydrofurans. Both steps are Ru-catalyzed, but the sequence requires only one precatalyst, because conversion of the metathesis catalyst into the dehydrogenation catalyst is achieved in situ, triggered by the oxidant tert-butyl hydroperoxide.
- Schmidt, Bernd,Krehl, Stefan,Jablowski, Eric
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supporting information; experimental part
p. 5119 - 5130
(2012/08/07)
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- Sequential combination of ruthenium-, base-, and gold-catalysis - A new approach to the synthesis of medicinally important heterocycles
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A general approach to the high-yielding synthesis of medicinally important heterocycles was achieved through the sequential combination of ring-closing metathesis, base-induced ring opening (BIRO), hydroamination, and a Diels-Alder reaction of functionalized allyl-(2-allylphenyl)amines in the presence of a catalytic amount of Grubbs' second-generation catalyst, base (tBuOK), and [AuCl(PPh3)]/AgOTf. Herein, we also demonstrate the important electronic factors in the BIRO of N-substituted-benzo[b]azepines for the regioselective synthesis of functionalized (Z)-N-substituted-2-(buta-1,3-dienyl) phenylamines in very good yields with high purity; these are very good, useful compounds in medicinal chemistry. We also discovered the selective cascade synthesis of privileged hexahydrophenanthridines from (Z)-N-substituted-2-(buta- 1,3-dienyl)phenylamines by gold catalysis in moderate to good yields with >99 % diastereomeric excess. The possible reaction mechanism for the unusual hydroamination followed by [4+2] cycloaddition of functionalized (Z)-N-substituted-2-(buta-1,3-dienyl)phenylamines through gold catalysis is discussed in this work. A novel process for the synthesis of highly substituted, medicinally important heterocycles was achieved through the sequential combination of ring-closing methathesis, base-induced ring opening, hydroamination, and Diels-Alder reaction of functionalized allyl-(2-allylphenyl) amines in the presence of a catalytic amount of [Ru], base, and [Au] (see scheme). Copyright
- Ramachary, Dhevalapally B.,Narayana, Vidadala V.
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supporting information; experimental part
p. 3514 - 3522
(2011/08/06)
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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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- Efficient regio- And stereoselective formation of azocan-2-ones via 8-endo cyclization of α-carbamoyl radicals
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The iodine-atom-transfer 8-endo cyclization of α-carbamoyl radicals was investigated experimentally and theoretically. With the aid of Mg(CIO 4)2 and a bis(oxazoline) ligand, N- ethoxycarbonylsubstituted N-(pent-4-enyl)-2-iodoalkanamides underwent 8-endo cyclization leading to the formation of only the corresponding 3,5-trans-substituted azocan-2-ones in excellent yields. Similarly, the BF 3·OEt2/H2O-promoted reactions of N-ethoxycarbonyl-N-(2-allylaryl)-2-iodoalkanamides afforded exclusively the benzazocanone products with a 3,5-cis configuration in high yields. The bidentate chelation of substrate radicals not only significantly improved the efficiency of cyclization but also resulted in the change of stereochemistry of azocanone products from 3,8-iransto 3,8-cis. Theoretical calculations at the UB3LYP/6-31G* level revealed that the cyclization of N-carbonyl- substituted α-carbamoyl radicals occurs via the E-conformational transition states without the presence of a Lewis acid. On the other hand, the cyclization proceeds via the Z-conformational transition states when the substrates form the bidentate chelation with a Lewis acid. In both cases, the 8-endo cyclization is always fundamentally preferred over the corresponding 7-exo cyclization. The complexed radicals having the more rigid conformations also allow the better stereochemical control in the iodine-atom-abstraction step. To further understand the reactivity of a-carbamoyl radicals, the competition between the 8-endo and 5-exo cyclization was also studied. The results demonstrated that the 8-endo cyclization is of comparable rate to the corresponding 5-exo cyclization for a-carbamoyl radicals with fixed Z-conformational transition states. As a comparison, the 8-endo mode is fundamentally preferred over the 5-exo mode in the cyclization of NH-amide substrates because the latter requires the Z-conformational transition states, whereas the former proceeds via the more stable E-conformational transition states.
- Fang, Xinqiang,Liu, Kun,Li, Chaozhong
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supporting information; experimental part
p. 2274 - 2283
(2010/05/01)
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- Facile access to bicyclic sultams with methyl 1-sulfonylcyclopropane-l- carboxylate moieties
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N-(2,3-Dibromopropyl)- and N-(3,4-dibromobutyl)(methoxycarbonyl) methanesulfanilides upon treatment with potassium carbonate in DMF furnish, methyl 3-aryl-2,2-dioxo-2thia-3-azabicyclo[n.1.0]alkane-1.-carboxylates in yields ranging from 54 to 84% (10 examples). The starting materials were obtained by sulfonylation of N-alkenylanilines with methyl (chlorosulfonyl) acetate and. subsequent bromination. For the N-alkenylanil.in.es (10 examples, 60-77% yield) an efficient new synthesis employing a 2-nitrophenylsulfonyl substituent as a protective as well as an activating group has been developed. The 4-methoxyphenyl (PMP) group could easily be removed, from, the sultam. nitrogen atom by treatment with cerium(IV) ammonium nitrate.
- Rassadin, Valentin A.,Tomashevskiy, Aleksandr A.,Sokolov, Viktor V.,Ringe, Arne,Magull, Joerg,De Meijere, Armin
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experimental part
p. 2635 - 2641
(2009/11/30)
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- Palladium-catalyzed cyclization/cyclopropanation reaction for the synthesis of fused N-containing heterocycles
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Palladium-catalyzed cyclization/cyclopropanation can be used to convert a range of substituted cyclic N-aryl allyl/methallyl amines efficiently and selectively to the corresponding fused tetrahydropyridine/cyclopropane-fused isoquinoline derivatives via β
- Nandi, Sukla,Ray, Jayanta K.
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scheme or table
p. 6993 - 6997
(2010/02/27)
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- Oxidative diamination of alkenes with ureas as nitrogen sources: Mechanistic pathways in the presence of a high oxidation state palladium catalyst
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A first palladium-catalyzed intramolecular diamination of unfunctionalized terminal alkenes has recently been reported. This study investigates the details of its mechanistic course based on NMR titration, kinetic measurements competition experiments, and deuterium labeling. It concludes a two-step procedure consisting of syn-aminopalladation with an unligated palladium(II) catalyst state followed by oxidation to palladium(IV) and subsequent C-N bond formation to give the final products as cyclic diamines. Related reactions employing sulfamides give rise to aminoalkoxy-functionalization of alkenes. This process was investigated employing deuterated alkenes and found to follow an identical mechanism where stereochemistry is concerned. It exemplifies the importance of cationic palladium(IV) intermediates prior to the final reductive elimination from palladium and proves that the nucelophile for this step stems from the immediate coordination sphere of the palladium(IV) precursor. These results have important implications for the general development of alkene 1,2-difunctionalization and for the individual processes of aminopalladation and palladium-catalyzed Calkyl-N bond formation.
- Muniz, Kilian,Hoevelmann, Claas H.,Streuff, Jan
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p. 763 - 773
(2008/09/19)
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- Pd(II)-catalyzed enantioselective oxidative tandem cyclization reactions. Synthesis of indolines through C-N and C-C bond formation
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We have developed an efficient Pd(II)-catalyzed enantioselective oxidative tandem cyclization strategy using molecular oxygen as a green oxidant for the double 5-exo-trig cyclizations of N-(2-allylaryl) amides to afford a variety of indolines in good yiel
- Yip, Kai-Tai,Yang, Min,Law, Ka-Lun,Zhu, Nian-Yong,Yang, Dan
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p. 3130 - 3131
(2007/10/03)
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- An improved method of synthesis of precursors for amino-Claisen rearrangement
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N-Allylarylamines are useful precursors in amino-Claisen rearrangements affording 2-allylarylamines in one step. An improved method for the synthesis of a series of N-allylarylamines (2a-h) has been described.
- Jain, Seema,Pandey, Neelesh,Kishore
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p. 1052 - 1054
(2007/10/03)
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- TRICYCLIC BENZAZEPINE DERIVATIVES AS SQUALENE SYNTHASE INHIBITORS USED FOR THE TREATMENT OF CARDIOVASCULAR DISEASES
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The invention relates to novel tricyclic benzazepine derivatives of formula (I), methods for the production thereof, the use thereof for treating and/or preventing diseases, and the use thereof for producing medicaments used for the treatment and/or prophylaxis of diseases, preferably cardiovascular diseases, particularly dyslipidemia, arteriosclerosis, restenosis, and ischemia.
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Page/Page column 40
(2008/06/13)
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- Novel strategies for the solid phase synthesis of substituted indolines and indoles
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Using a polymer-bound selenenyl bromide resin, o-allyl and o-prenyl anilines were cycloaded to afford a series of solid-supported indoline and indole scaffolds. These scaffolds were then functionalized and cleaved via four distinct methods, namely traceless reduction, radical cyclization, radical rearrangement, and oxidative elimination, to afford 2-methyl indolines, polycyclic indolines, 2-methyl indoles, and 2-propenyl indolines, respectively. A number of small combinatorial libraries of compounds reminiscent of certain designed ligands of biological interest were constructed demonstrating the potential utility of the developed methodology to chemical biology studies and the drug discovery process.
- Nicolaou,Roecker,Hughes, Robert,Van Summeren, Ruben,Pfefferkorn, Jeffrey A.,Winssinger, Nicolas
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p. 465 - 476
(2007/10/03)
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- Reaction of primary aromatic amines with alkyl carbonates over NaY faujasite: A convenient and selective access to mono-N-alkyl anilines
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At atmospheric pressure and at 130-160°C, primary aromatic amines (p-XC6H4NH2, X = H, Cl, NO2) are mono-N-alkylated in a single step, with symmetrical and asymmetrical dialkyl carbonates [ROCOOR′, R = Me, R′ = MeO(CH2)2O(CH2)2; R = R′ = Et; R = R′ = benzyl; R = R′ = allyl; R = Et, R′ = MeO(CH2)2O(CH2)2], in the presence of a commercially available NaY faujasite. No solvents are required. Mono-N-alkyl anilines are obtained with a very high selectivity (90-97%), in good to excellent yields (68-94%), on a preparative scale. In the presence of triglyme as a solvent, the mono-N-alkyl selectivity is independent of concentration and polarity factors. The reaction probably takes place within the polar zeolite cavities, and through the combined effect of the dual acid-base properties of the catalyst.
- Selva,Tundo,Perosa
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p. 677 - 680
(2007/10/03)
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- Direct palladium-catalyzed selective monoallylation of anilines using allylic alcohols
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N-Allylation of anilines using allylic alcohols directly to give monoallylic anilines selectively in high yields has been realized by employing palladium acetate-triphenylphosphine as the catalyst. Palladium-catalyzed one-pot cyclization of 2-aminophenols with 2-butene-1,4-diol leads to 3,4-dihydro-2-vinyl-2H-1,4-benzoxazines. (C) 2000 Elsevier Science Ltd.
- Yang,Yu,Tsai
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p. 7097 - 7100
(2007/10/03)
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- Zinc Mediated Allylation of Azides: A Novel Method for the High Yield Preparation of N-Allylamines
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A quick and efficient approach for mono N-allylamines has been developed by the reaction of allyl zinc reagent with alkyl and aryl azides in DMF. - Keywords: azides; zinc; DMF; allylamine
- Kumar, H. M. Samapath,Anjaneyulu, S.,Reddy, B. V. Subba,Yadav, J. S.
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p. 551 - 552
(2007/10/03)
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- Palladium-catalyzed N-allylation of anilines by direct use of allyl alcohols in the presence of titanium(IV) isopropoxide
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The direct activation of C-O bonds in allyl alcohols by palladium complexes has been accelerated by carrying out the reactions in the presence of titanium(IV) isopropoxide and 4A molecular sieves. N-Allylation of anilines to give mono- and diallylanilines using allyl alcohols directly has been realized by employing palladium catalysts.
- Yang, Shyh-Chyun,Chung, Wen-Hung
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p. 953 - 956
(2007/10/03)
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- An efficient palladium-catalyzed route to N-allylanilines by the direct use of allyl alcohols
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The direct activation of C-O bonds in allyl alcohols by palladium complexes has been accelerated by carrying out the reactions in the presence of titanium(IV) isopropoxide and molecular sieves (4A). N-Allylation of anilines to give mono- and diallylanilines directly using allyl alcohols has been realized by employing palladium catalysts.
- Yang, Shyh-Chyun,Hung, Chung-Wei
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p. 1747 - 1752
(2007/10/03)
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- UNEXPECTED REACTIVITY OF ALLYL MAGNESIUM CHLORIDE WITH NITROARENES. A GENERAL METHOD OF SYNTHESIS OF N-ALLYL-N-ARYLHYDROXYLAMINES AND N-ALLYLANILINES.
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In contrast to alkyl Grinard reagents, the allyl reagent reacts with nitroarenes via 1,2 addition to the nitro group.The "in situ" treatment of the unstable intermediate adduct with LiAlH4 in the presence of catalytic Pd/C provides a general synthesis of N-allyl-N-arylhydroxylamines or N-allylanilines.
- Bartoli, Giuseppe,Marcantoni, Enrico,Bosco, Marcella,Dalpozzo, Renato
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p. 2251 - 2254
(2007/10/02)
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- TRANSFORMATION OF ALLYLSILANES INTO ALLYLAMINES VIA PHENYLTELLURINYLATION
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Allylsilanes were treated with benzenetellurinyl trifluoracetate below room temperature followed by amines at 65 deg.C in 1,2-dichloroethane in the presence of boron trifluoride etherate, readily giving allylamines.
- Hu, Nan X.,Aso, Yoshio,Otsubo, Tetsuo,Ogura, Fumio
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p. 4949 - 4952
(2007/10/02)
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- Synthese de N-Alkyl-arylamines par Thermolyse ou Photolyse d'Alkyl-3-diaryl-1,3-triazenes
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The thermolysis of 3-alkyl-1,3-bis(p-chlorophenyl)triazenes in benzene or methanol leads to the formation of N-alkyl-p-chloroanilines (2) in 19-50 percent yield, N-alkyl-bis(p-chlorophenyl)amines (3) in 7.5-15.5 percent yield and 4,4'-dichlorobiphenyle (4) in 1-7 percent yield; besides with benzene as the substrate, 4-chlorobiphenyle (5) (12-20 percent yield) was also formed.The photolysis in methanol gives only the N-alkyl-p-chloroanilines (2) in 32-40 percent yield.In these two cases the results are consistent with a radical pair formation in a solvent cage, recombination (thermolysis) and/or diffusion (thermolysis and photolysis) with intermolecular abstraction of hydrogen.A free radical chain mechanism is involved in the photolytic process and the quantum yield is high.
- Julliard, Michel,Vernin, Gaston,Metzger, Jacques
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p. 467 - 472
(2007/10/02)
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