- Amine compound as well as preparation method and application thereof
-
The invention discloses an amine compound containing allyl or benzyl as well as a preparation method and application of the amine compound. The preparation method comprises the steps of sequentially adding a raw material 1, amine, a catalyst and an additive into a reaction solvent, and stirring and reacting for 12-24 hours in an air atmosphere at the temperature of 50-120 DEG C to obtain a reaction solution, wherein the raw material 1 is allyl alcohol or benzyl alcohol, and the molar volume ratio of the raw material 1 to the amine to the catalyst to the additive to the reaction solvent is (0.2 to 8) mmol: (0.4 to 12) mmol: (0.01 to 0.4) mmol: (0.01 to 0.4) mmol: (2 to 40) mL; and removing the reaction solvent of the reaction solution, and then carrying out purification through thin layer chromatography/column chromatography, wherein a developing solvent system is petroleum ether/ethyl acetate, and the amine compound containing allyl or benzyl is obtained. The amine compound can be applied to preparation of framework of biological and pharmaceutical active molecules. The preparation method disclosed by the invention is wide in applicable substrate range, convenient to operate, green and environment-friendly.
- -
-
Paragraph 0037-0040
(2021/08/21)
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- Palladium-Catalyzed Regioselective and Stereospecific Ring-Opening Suzuki-Miyaura Arylative Cross-Coupling of 2-Arylazetidines with Arylboronic Acids
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We have developed a palladium-catalyzed regioselective and enantiospecific ring-opening Suzuki–Miyaura arylative cross-coupling of N-tosyl-2-arylazetidines to give enantioenriched 3,3-diarylpropylamines. This reaction represents an example of transition-metal-catalyzed ring-opening cross-coupling using azetidines as a non-classical alkyl electrophile. Density functional theory rationalized the mechanism of the full catalytic cycle, which consists of the selectivity-determining ring opening of the azetidine, reaction with water, rate-determining transmetalation, and reductive elimination. Transition states of the selectivity-determining ring-opening step were systematically determined by the multi-component artificial force induced reaction (MC-AFIR) method to explain the regioselectivity of the reaction. (Figure presented.).
- Takeda, Youhei,Toyoda, Kazuya,Sameera,Tohnai, Norimitsu,Minakata, Satoshi
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supporting information
p. 2796 - 2805
(2021/04/15)
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- Catalytic Diastereo- and Enantioselective Fluoroamination of Alkenes
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The stereoselective synthesis of syn-β-fluoroaziridine building blocks via chiral aryl iodide-catalyzed fluorination of allylic amines is reported. The method employs HF-pyridine as a nucleophilic fluoride source together with mCPBA as a stoichiometric oxidant, and affords access to arylethylamine derivatives featuring fluorine-containing stereocenters in high diastereo- and enantioselectivity. Catalyst-controlled diastereoselectivity in the fluorination of chiral allylic amines enabled the preparation of highly enantioenriched 1,3-difluoro-2-amines bearing three contiguous stereocenters. The enantioselective catalytic method was applied successfully to other classes of multifunctional alkene substrates to afford anti-β-fluoropyrrolidines, as well as a variety of 1,2-oxyfluorinated products.
- Mennie, Katrina M.,Banik, Steven M.,Reichert, Elaine C.,Jacobsen, Eric N.
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p. 4797 - 4802
(2018/04/17)
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- Regioselective Intermolecular Allylic C?H Amination of Disubstituted Olefins via Rhodium/π-Allyl Intermediates
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A method for catalytic intermolecular allylic C?H amination of trans-disubstituted olefins is reported. The reaction is efficient for a range of common nitrogen nucleophiles bearing one electron-withdrawing group, and proceeds under mild reaction conditions. Good levels of regioselectivity are observed for a wide range of electronically diverse trans-β-alkyl styrene substrates.
- Burman, Jacob S.,Blakey, Simon B.
-
supporting information
p. 13666 - 13669
(2017/10/24)
-
- Ni-Catalyzed regio- and stereoselective addition of arylboronic acids to terminal alkynes with a directing group tether
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Addition of arylboronic acids to directing group tethered acetylenes in a regio and stereoselective manner using an inexpensive catalytic system is achieved for the first time to access highly sought after allyl/homoallyl alcohol/amine units. The apparent vinylnickel intermediate was successfully trapped by the Michael electrophiles to get defined tri- and tetra-substituted olefins. An interesting selectivity switch was observed with internal alkynes.
- Hari Babu, Madala,Ranjith Kumar, Gadi,Kant, Ruchir,Sridhar Reddy, Maddi
-
supporting information
p. 3894 - 3897
(2017/04/04)
-
- Cobalt-catalyzed (Z)-selective semihydrogenation of alkynes with molecular hydrogen
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Cobalt-catalyzed highly (Z)-selective semihydrogenation of alkynes using molecular H2 was developed using commercially available and cheap cobalt precursors. A variety of (Z)-alkenes were obtained in moderate to excellent selectivities [(Z)-alkene/(E)-alkene/alkane ratio up to >99 : 1 : 1] and it was found that the readily available ethylenediamine ligand is crucial in determining the selectivity.
- Chen, Caiyou,Huang, Yi,Zhang, Zongpeng,Dong, Xiu-Qin,Zhang, Xumu
-
supporting information
p. 4612 - 4615
(2017/04/28)
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- Chiral Br?nsted Acid Catalyzed Enantioselective Phosphonylation of Allylamine via Oxidative Dehydrogenation Coupling
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A new strategy for the synthesis of chiral α-amino phosphonates by enantioselective C-H phosphonylation of allylamine with phosphite in the presence of a chiral Br?nsted acid catalyst has been developed. This protocol successfully integrates direct C-H oxidation with asymmetric phosphonylation and exhibits high enantioselectivity.
- Cheng, Ming-Xing,Ma, Ran-Song,Yang, Qiang,Yang, Shang-Dong
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p. 3262 - 3265
(2016/07/13)
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- Rhodium-Catalyzed [5+2] Cycloaddition of 3-Acyloxy-1,4-enyne with Alkene or Allene
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We recently developed a completely new type of Rh-catalyzed [5+2] cycloaddition by using 3-acyloxy-1,4-enyne (ACE) as the 5-carbon building block. In this update, we show that ACE can undergo intramolecular [5+2] cycloaddition with either an alkene or an allene in the presence of an appropriate rhodium catalyst and ligands to afford bicyclic compounds with multiple stereogenic centers. In most cases, cis-fused bicyclo[5.3.0]decadienes are prepared highly diastereoselectively. (Figure presented.) .
- Song, Wangze,Lynch, John C.,Shu, Xing-Zhong,Tang, Weiping
-
supporting information
p. 2007 - 2011
(2016/07/06)
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- Rhodium/Yanphos-Catalyzed Asymmetric Interrupted Intramolecular Hydroaminomethylation of trans-1,2-Disubstituted Alkenes
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The first interrupted asymmetric hydroaminomethylation reaction was developed. The challenging trans-1,2-disubstituted olefins were employed as substrates, and a series of valuable chiral pyrrolidinones and pyrrolidines were obtained in high yields with high regioselectivities and excellent enantioselectivities. Several synthetic transformations were conducted, demonstrating the high synthetic utility of our method. A creative route for the synthesis of vernakalant and Enablex was also developed.
- Chen, Caiyou,Jin, Shicheng,Zhang, Zhefan,Wei, Biao,Wang, Heng,Zhang, Kai,Lv, Hui,Dong, Xiu-Qin,Zhang, Xumu
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p. 9017 - 9020
(2016/08/05)
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- A Ruthenium/Phosphoramidite-Catalyzed Asymmetric Interrupted Metallo-ene Reaction
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Allylic chlorides prepared from commercially available trans-1,4-dichloro-2-butene were converted to trans-disubstituted 5- and 6-membered ring systems with perfect diastereoselectivity and high enantioselectivity under chiral ruthenium catalysis. These products contain stereodefined secondary and tertiary alcohols that originate from the trapping of an alkylruthenium intermediate with adventitious water. Key to the success of this transformation was the development of a new BINOL-based phosphoramidite ligand containing bulky substitution at its 3- and 3′-positions. As a demonstration of product utility, diastereoselective Friedel-Crafts reactions were performed on the chiral benzylic alcohols in high yield and stereoselectivity.
- Trost, Barry M.,Ryan, Michael C.
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p. 2981 - 2984
(2016/03/19)
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- Iron oxide-silver magnetic nanoparticles as simple heterogeneous catalysts for the direct inter/intramolecular nucleophilic substitution of π-activated alcohols with electron-deficient amines
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The development of bimetallic iron oxide-silver magnetic nanoparticles (Fe2O3-Ag MNPs) catalytic system provides an efficient heterogeneous synthetic pathway to allylic amines and 1,2-dihydroquinolines involving the direct inter/intramolecular nucleophilic substitution of π-activated alcohols with electron-deficient amines. The major advantages of the present method are wide substrate scope, simple product separation, low catalyst loading, and magnetically recyclable catalyst.
- Xu, Xingzhu,Wu, Haibo,Li, Zhengyi,Sun, Xiaoqiang,Wang, Zhiming
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p. 5254 - 5259
(2015/07/15)
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- Multimetallic Ir-Sn3-catalyzed substitution reaction of π-activated alcohols with carbon and heteroatom nucleophiles
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An atom economic and catalytic substitution reaction of π-activated alcohols by a multimetallic IreSn3 complex has been demonstrated. The multimetallic IreSn3 complex can be easily synthesized from the reaction between [Cp*IrCl2]2 and SnCl2. In presence of as little as 1 mol % of the catalyst three different types of π-activated alcohols, namely benzyl, allyl, and propargyl alcohols, have been successfully transformed into alkylated products using carbon (arenes, heteroarenes, allyltrimethylsilane, and 1,3-dicarbonyls), nitrogen (sulfonamides), oxygen (alcohols), and sulfur (thiols) nucleophiles in very high yields. An electrophilic mechanism is proposed from the Hammett correlation study.
- Maity, Arnab Kumar,Chatterjee, Paresh Nath,Roy, Sujit
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p. 942 - 956
(2013/07/25)
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- Nanoporous gold catalyst for highly selective semihydrogenation of alkynes: Remarkable effect of amine additives
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We report for the first time the highly selective semihydrogenation of alkynes using the unsupported nanoporous gold (AuNPore) as a catalyst and organosilanes with water as a hydrogen source. Under the optimized reaction conditions, the present semihydrogenation of various terminal- and internal-alkynes affords the corresponding alkenes in high chemical yields and excellent Z-selectivity without any over-reduced alkanes. The use of DMF as solvent, which generates amines in situ, or pyridine as an additive is crucial to suppress the association of hydrogen atoms on AuNPore to form H2 gas, which is unable to reduce alkynes on the unsupported gold catalysts. The AuNPore catalyst can be readily recovered and reused without any loss of catalytic activity. In addition, the SEM and TEM characterization of nanoporosity show that the AuNPore catalyst has a bicontinuous 3D structure and a high density of atomic steps and kinks on ligament surfaces, which should be one of the important origins of catalytic activity.
- Yan, Mei,Jin, Tienan,Ishikawa, Yoshifumi,Fujita, Takeshi,Chen, Lu-Yang,Asao, Naoki,Chen, Ming-Wei,Yamamoto, Yoshinori,Minato, Taketoshi,Bao, Ming
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p. 17536 - 17542,7
(2020/09/16)
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- FeCl3·6H2O and TfOH as catalysts for allylic amination reaction: A comparative study
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The use of FeCl3·6H2O and TfOH as readily available and easy-to-handle catalysts for the direct allylic amination reaction using a wide variety of nitrogenated nucleophiles onto different free allylic alcohols is described. Comparative studies between these catalysts, as representative Lewis and Bronsted acids are conducted, concluding that both are suitable catalysts for this transformation. The reactions are performed in a flask open to air and using technical grade 1,4-dioxane. In light of the results obtained from this study it can be asserted that TfOH turned out to be slightly superior than the FeIII salt since similar or better yields are obtained in most of the cases using lower catalyst loadings and milder reaction conditions. A similar trend is observed when carbonucleophiles were employed in the allylic substitution reaction. Studies for the elucidation of the reaction mechanism are in agreement with a carbocationic intermediate, being the regioselectivity governed by the stability of the final product. Copyright
- Trillo, Paz,Baeza, Alejandro,Najera, Carmen
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experimental part
p. 2929 - 2934
(2012/06/29)
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- Rhodium-catalyzed aerobic N-alkylation of sulfonamides with alcohols
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By using the famous Wilkinson's catalyst, N-alkylation of sulfonamides can be easily realized under mild aerobic conditions by using alcohols as the alkylating reagent, giving monoalkylated sulfonamides in high yields and selectivities with water produced as the only byproduct. This advantageous aerobic method is potentially general in substrate scope that it can also be applied to other amides, amines and alcohols.
- Feng, Sun Lin,Liu, Chuan Zhi,Li, Qiang,Yu, Xiao Chun,Xu, Qing
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scheme or table
p. 1021 - 1024
(2012/06/01)
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- Substrate-directable heck reactions with arenediazonium salts. The regio- and stereoselective arylation of allylamine derivatives and applications in the synthesis of naftifine and abamines
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The palladium-catalyzed, substrate-directable Heck-Matsuda reaction of allylamine derivatives with arenediazonium salts is reported. The reaction proceeds under mild conditions, with excellent regio- and stereochemical control as a function of coordinating groups present in the allylamine substrate. The distance between the olefin moiety and the car-bonylic system seems to play a key role regarding the regiocontrol. The method presents itself as robust, as simple to carry out, and with wide synthetic scope concerning the allylic substrates and the type of arenediazonium employed. The synthetic potential of the method is illustrated by the short total syntheses of the bioactive compounds naftifine, abamine, and abamine SG.
- Prediger, Patricia,Barbosa, Lais Ferreira,Genisson, Yves,Correia, Carlos Roque Duarte
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p. 7737 - 7749
(2011/12/01)
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- Cross-coupling of grignard reagents with sulfonyl-activated sp3 carbon-nitrogen bonds
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Sulfonyl-activated sp3 carbon-nitrogen bonds have been found to be cleaved by Grignard reagents in the presence of 5 mol% of copper(I) iodide (CuI). Significantly, a broad range of sulfonyl-activated benzylic, allylic, and propargylic amines smoothly undergo the cross-coupling reaction with Grignard reagents to afford structurally diverse coupling products in good to excellent yields and with high chemo-, regio-, and stereoselectivity. Moreover, an S N2 mechanism has been demonstrated to be involved in the cross-coupling reaction that allows the asymmetric synthesis of chiral hydrocarbons from optically active α-branched amine derivatives. Copyright
- Li, Man-Bo,Tang, Xiang-Ling,Tian, Shi-Kai
-
supporting information; experimental part
p. 1980 - 1984
(2011/10/12)
-
- Integrated electrochemical-chemical oxidation mediated by alkoxysulfonium Ions
-
Generation of carbocations by the "cation pool" method followed by reaction with dimethyl sulfoxide (DMSO) gave the corresponding alkoxysulfonium ions. Alkoxysulfonium ions could also be generated by in situ DMSO trapping of electrochemically generated carbocations. The resulting alkoxysulfonium ions were transformed into carbonyl compounds by treatment with triethylamine. The present integrated electrochemical-chemical oxidation can be applied to the oxidation of diarylmethanes to diaryl ketones, toluenes to benzaldehydes, and aryl-substituted alkenes to 1,2-diketones. Moreover, the oxidation of unsaturated compounds bearing a nucleophilic group in an appropriate position gives cyclized carbonyl compounds.
- Ashikari, Yosuke,Nokami, Toshiki,Yoshida, Jun-Ichi
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p. 11840 - 11843
(2011/09/21)
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- Bicyclic cyclopentenones via the combination of an iridium-catalyzed allylic substitution with a diastereoselective intramolecular pauson-khand reaction
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Enantioselective syntheses of bicyclic cyclopentenones are described. Key steps are an iridium-catalyzed allylic substitution and an intramolecular diastereoselective Pauson-Khand reaction. The diastereoselectivity of the Pauson-Khand reaction was found t
- Farwick, Andreas,Engelhart, Jens U.,Tverskoy, Olena,Welter, Carolin,Umlauf Nee Stang, Quendolin A.,Rominger, Frank,Kerr, William J.,Helmchen, Guenter
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experimental part
p. 349 - 370
(2011/04/18)
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- Gold(I)-catalyzed highly regio- and stereoselective decarboxylative amination of allylic N-tosylcarbamates via base-induced aza-Claisen rearrangement in water
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(Figure Presented)A gold(l)-catalyzed decarboxylative animation of allylic N-tosylcarbamates via base-induced aza-Claisen rearrangement has been developed. A variety of substituted W-tosyl allylic amines were obtained In good yield, excellent regloselectlvity, and high to excellent stereoselectivity. This transformation could be performed either in H2O or In one pot directly from allylic alcohols and therefore represents an efficient and environmentally benign protocol for the synthesis of N-tosyl allylic amines.
- Xing, Dong,Yang, Dan
-
supporting information; experimental part
p. 1068 - 1071
(2010/06/13)
-
- Lewis acid-mediated unprecedented ring-opening rearrangement of 2-Aryl-N-tosylazetidines to enantiopure (E)-allylamines
-
A highly efficient strategy for Cu(OTf)2-mediated ring-opening of 2-aryl-N-Mosylazetidines in polar and coordinating solvents followed by an unprecedented rearrangement to substituted achiral and chiral (E)-allylamines (ee >99%) is reported. Th
- Ghorai, Manas K.,Kumar, Amit,Das, Kalpataru
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p. 5441 - 5444
(2008/09/18)
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- Lewis acid mediated SN2-type nucleophilic ring opening followed by [4+2] cycloaddition of N-tosylazetidines with aldehydes and ketones: synthesis of chiral 1,3-oxazinanes and 1,3-amino alcohols
-
A highly efficient strategy for Cu(OTf)2 mediated SN2-type nucleophilic ring opening followed by [4+2] cycloaddition reactions of enantiopure 2-phenyl-N-tosylazetidines with various aldehydes and ketones afforded a variety of substit
- Ghorai, Manas K.,Das, Kalpataru,Kumar, Amit
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p. 4373 - 4377
(2008/02/04)
-
- On the mechanism of carbohydroxypalladation of enynes. Additional insights on the cyclization of enynes with electrophilic metal complexes
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Different mechanisms have been proposed for the cyclization of enynes catalyzed by electrophilic metal halides or complexes. We present evidence to indicate that the previously reported "carbohydroxypalladation" and the "hydroxycyclization catalyzed by PtII" are closely related reactions. Thus, palladium complexes formed in situ from PdCl2 and trisulfonated phosphane TPPTS or cyclic phosphite P(OCH2)3CEt as the ligands catalyze the methoxy- or hydroxycyclization of enynes with selectivities similar to those observed with PtII complexes. Deuteration studies indicate that activation of the alkyne by PdII promotes an anti-addition of the alkene. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
- Nevado, Cristina,Charruault, Lise,Michelet, Veronique,Nieto-Oberhuber, Cristina,Paz Munoz,Mendez, Maria,Rager, Marie-Noelle,Genet, Jean-Pierre,Echavarren, Antonio M.
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p. 706 - 713
(2007/10/03)
-
- Tellurium-triggered formation of racemic and non-racemic allylic amines from aziridinemethanol derivatives
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Sharpless epoxidation, aminohydroxylation, and aziridination procedures provide substrates for the tellurium-triggered synthesis of racemic and non-racemic allylic amines under phase-transfer conditions.
- Chao, Bin,Dittmer, Donald C.
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p. 5789 - 5791
(2007/10/03)
-
- Amidation of saturated C-H bonds catalyzed by electron-deficient ruthenium and manganese porphyrins. A highly catalytic nitrogen atom transfer process
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(equation presented) Amidation of a variety of hydrocarbons with PhI=NTs catalyzed by ruthenium and manganese meso-tetrakis(pentafluorophenyl)porphyrins 1 and 2 afforded N-substituted amides in up to 92% yields with good to excellent substrate conversions. By employing catalyst 2, exceptionally high turnovers (up to 2600) were achieved, and the amidations can be effected by directly using PhI(OAc)2/NH2R as amidating reagents; in the case of R = COCF3 a direct amination was realized in up to 90% yield.
- Yu, Xiao-Qi,Huang, Jie-Sheng,Zhou, Xiang-Ge,Che, Chi-Ming
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p. 2233 - 2236
(2007/10/03)
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- A facile highly regio- and stereoselective preparation of N-tosyl allylic amines from allylic alcohols and tosyl isocyanate via palladium(II)-catalyzed aminopalladation-β-heteroatom elimination
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(equation presented) The high regio- and stereoselectivity have been obtained from the allylic substitution reaction catalyzed by palladium(II) species. From allylic alcohols, one-pot reaction with tosyl isocyanate followed by palladium(II)-catalyzed ally
- Lei, Aiwen,Lu, Xiyan
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p. 2357 - 2360
(2007/10/03)
-
- Preparation of azetidines by 4-endo trig cyclizations of N-cinnamyl tosylamides
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Formation of azetidines by electrophilic cyclizations have been reported, starting with homoallylic amines (4-exo mode cyclizations). We reported that the formation of these compounds can be carried out starting with allylic amines (4-endo mode cyclizations) using bis(collidine)bromonium(I) hexafluorophosphate as an electrophile. These cyclizations occur via a carbocation intermediate.
- Robin, Sylvie,Rousseau, Gerard
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p. 3007 - 3011
(2007/10/03)
-
- Deprotection of sulfonyl aziridines
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The deprotection of the chiral N-sulfonyl aziridines 1-3 has been studied under different desulfonylation conditions. Two methods for the efficient aleprotection of 2-benzyl-, 2-phenyl-, and 2-carboxyl-N- sulfonylaziridines were found. The desulfonylation with lithium and a catalytic amount of di-tert-butyl biphenyl in THF at -78 °C led to the corresponding NH aziridines with yields up to 85%. Alternatively, the desulfonylation could be carried out with magnesium in methanol under ultrasonic conditions. The latter proved to be a very mild method and afforded the desulfonylated aziridines with yields up to 75%, even when the 2-phenyl substituted aziridine 2 was the studied substrate. Furthermore, in all the cases studied, no racemization was observed in the chiral center of the aziridines.
- Alonso, Diego A.,Andersson, Pher G.
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p. 9455 - 9461
(2007/10/03)
-
- On the faciality of intramolecular Palladium(0)-Catalysed 'metallo-ene-type' cyclisations
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The palladium-calalysed 'metallo-ene' step in a cyclisation/β-elimination reaction sequence has been shown to be suprafacial with respect to the olefinic component. This reaction has been applied to the synthesis of a trisubstituted exocyclic alkenyl pyrrolidine with complete stereocontrol.
- Oppolzer, Wolfgang,Stammen, Blanda
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p. 3577 - 3586
(2007/10/03)
-
- The two component palladium catalyst system for intermolecular hydroamination of allenes
-
The combination of acetic acid with Pd2(dba)3.CHCl3 and dppf [1.1'-Bis(diphenylphosphino ferrocene)] is a new type of catalytic system, capable of effecting the addition of protected and/or functionalized amines to allenes
- Al-Masum, Mohammad,Meguro, Masaki,Yamamoto, Yoshinori
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p. 6071 - 6074
(2007/10/03)
-
- Palladium-catalyzed rearrangement of allylic sulfoximines: Application to the asymmetric synthesis of chiral allylic amines
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The palladium(0)-catalyzed reactions of the primary and secondary allylic sulfoximines 7, 9, 11, 13, 15, 17, and 19 gives allylic sulfinamides without 1,3-allylic rearrangement. These compounds were not isolated but were converted to their corresponding N-tosyl allylic amines, primary and secondary 8, 10, 12, 14, 16, 18, and 20, respectively. In the case of the optically active secondary allylic sulfoximines 17 and 19, chiral N-tosyl allylic secondary amines were formed in high enantiomeric purities.
- Pyne, Stephen G.,Dong, Zemin
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p. 5517 - 5522
(2007/10/03)
-
- High Chirality Transfer in Chiral Selenimides via Sigmatropic Rearrangement
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The imination of chiral cinnamyl 2-(1-dimethylaminoethyl)ferrocenyl selenides with phenyliodinane and chloramine-T affords the corresponding chiral allylic amines via sigmatropic rearrangement of the selenimide intermediates with up to 87percent ee, highly diastereoselective imination of selenides and highly stereospecific sigmatropic rearrangement being shown.
- Nishibayashi, Yoshiaki,Chiba, Takashi,Ohe, Kouichi,Uemura, Sakae
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p. 1243 - 1244
(2007/10/02)
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- Palladium catalyzed arylation of N-alkyl O-allyl carbamates: Synthesis of cinnamyl alcohols via Heck arylation
-
N-alkyl O-cinnamyl carbamates (3) were prepared in good yields by palladium catalyzed arylation of N-alkyl O-allyl carbamates (2) with aryl iodides.
- Ono, Keiji,Fugami, Keigo,Tanaka, Shuji,Tamaru, Yoshinao
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p. 4133 - 4136
(2007/10/02)
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- Amidoselenation of Olefins Using p-Toluenesulfonamide as a Nitrogen Nucleophile
-
The reaction of olefins, benzeneselenenyl chloride, and p-toluenesulfonamide in the presence of zinc(II) chloride affords N--p-toluenesulfonamides in good to excellent yields.When combined with alkylation on the carbon atom bearing the phenylseleno group thus introduced and subsequent oxidative or reductive removal of the selenium moiety, this reaction can be utilized in the preparation of a wide range of allylic or saturated amides.
- Toshimitsu, Akio,Kusumoto, Takehiro,Oida, Tatsuo,Tanimoto, Shigeo
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p. 2148 - 2152
(2007/10/02)
-
- A New Method for Radical Generation: Reductive C-Se or C-S Bond Cleavage of Cyclic Onium Salts
-
2-Methyl-3,4-dihydro-1H-2-benzoselenopyranium salt (1) was reduced by some metallic reagents or magnesium metal via the single-electron transfer (SET) process to give 2--toluene (2).Magnesium metal was a good SET reducing agent.Some other selenonium or sulphonium salts (7), (14), (22), (27) and (32) were similarly reduced by magnesium.Particularly, sonication accelerated the reductions. ε-Eneselenonium salt (43) was treated with activated magnesium to give a cyclised pyrrolidine derivative (44).
- Kataoka, Tadashi,Tsutsumi, Kazuhiro,Kano, Kenji,Mori, Kazuya,Miyake, Miho,et al.
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p. 3017 - 3025
(2007/10/02)
-
- One-Pot Synthesis of Tetrahydrofuran Derivatives from Allylic Alcohols and Vinyl Ethers by Means of Palladium(II) Acetate
-
Reaction of allylic alcohol with vinyl ether in the presence of Pd(OAc)2 afforded furan derivatives in good yield.Pd(OAc)2 was essential for the reaction.PdCl2 complex did not afford cyclized product but gave acetal exclusively.Three components were combined at once to produce 4-(3-butenyl)-2-butoxy-4-methyltetrahydrofuran upon treatment of a mixture of 2-methyl-2-propen-1-ol, butyl vinyl ether, and allyl bromide.The reaction could successfully be extended to the synthesis of nitrogen containing heterocycles by use of N-tosyl allylic amines in place of allylic alcohols.
- Fugami, Keigo,Oshima, Koichiro,Utimoto, Kiitiro
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p. 2050 - 2054
(2007/10/02)
-
- REACTIONS OF N-SULFINYL-p-TOLUENESULFONAMIDE WITH ALCOHOLS
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N-Sulfinyl-p-toluenesulfonamide (1) reacted with triaryl- and diarylmethanols to give predominantly N-substituted sulfonamides and SO2 presumably via carbonium ion intermediates.When carbonium ion forming alcohols, such as t-BuOH and Ph2C(Me)OH, were used, the predominant products were alkenes and p-toluenesulfonamide.Allylic alcohols afforded N-substituted sulfonamides, along with dienes and p-toluenesulfonamide.Alcohols wich could not predictably give relatively stable intermediate carbonium ions, gave either dialkyl sulfites or dialkyl ethers, along with p-toluenesulfonamide.In one case, namely with 9-phenylfluorenol, the 1:1 adduct with 1 (an amidosulfite) was isolated.A mechanism for the reaction is proposed.
- McFarland, John W.,Schut, Dirk,Zwanenburg, Binne
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p. 389 - 393
(2007/10/02)
-
- The Chemistry of Sulfur Diimides, 8. - Ene Reactions with Sulfur Diimides - Structure of the Ene Components and Reactivity in the Reaction with Ditosyl Sulfur Diimide
-
N,N'-Ditosyl sulfur diimide (1) is an exceptionally reactive enophilic compound.Its reactions with many allylic derivatives give sulfinamidines 3 or - by sigmatropic rearrangements of 3 - diamino sulfane derivatives 4, respectively, in good yields.Conclus
- Bussas, Reinhard,Kresze, Guenter
-
p. 629 - 649
(2007/10/02)
-