- Palladium and nickel complexes of (P,N)-ligands based on quinolines: Catalytic activity for polymerization and oligomerization
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Four (P,N)-ligands (1-4) with different steric and electronic properties were synthesized. They were used to prepare the monocationic palladium complexes [Pd(P,N)(CH3)(NCCH3)](PF6) (9-12). The structures of the newly prepared ligand 3 and the neutral palladium complex [Pd(P,N)(CH3)Cl] (10) were analysed by X-ray. The catalytic activity of the palladium complexes toward the copolymerization of styrene and ethylene with CO was low or non-existent. The nickel complexes [Ni(P,N)(1-naphthyl)Cl] (13-16), modified with the ligands 1-4, were prepared and their catalytic activity toward ethylene oligomerization was studied. They showed high activity at ambient temperature and low ethylene pressure (1-12 bar) in the presence of MAO.
- Sirbu, Doina,Consiglio, Giambattista,Gischig, Sebastian
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Read Online
- Preparation, Characterization, and Reactivity of Aliphatic Amino Iodane(III) Reagents
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The preparation of a new class of aliphatic amino iodane(III) reagents has been realized with the N-TMS?amine and acetoxybenziodazole participated in the formation of N?I bond. The amino-containing iodane(III) reagent 2 d was characterized by single-crystal X-ray diffraction, which revealed the expected hypervalent iodane distorted T-shaped geometry. A practical copper-catalyzed, directed electrophilic amination of aryl amines employing amino-iodane(III) as amination agents was disclosed that proceeded smoothly without external additives.
- Zhang, Yue,Lu, Jing,Lan, Tianlei,Cheng, Shaoling,Liu, Wei,Chen, Chao
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supporting information
p. 436 - 442
(2020/12/21)
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- An Alumino-Mannich Reaction of Organoaluminum Reagents, Silylated Amines, and Aldehydes
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A multi-component coupling using organoaluminum reagents, silylated amines, and aldehydes results in the formation of tertiary amines. Both alkenyl- and alkylaluminum reagents undergo reaction with iminium ion substrates for which the corresponding Petasis borono-Mannich reactions are unsuccessful.
- Tarasewicz, Anika,Ensan, Deeba,Batey, Robert A.
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supporting information
p. 6071 - 6074
(2018/04/27)
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- Nucleophilic bromodifluoromethylation of iminium ions
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A method for bromodifluoromethylation of iminium ions using Me3SiCF2Br is described. The reaction involves room temperature activation of the silicon reagent by HMPA to generate difluorocarbene, which upon interacting with excess of bromide ion provides bromodifluoromethyl carbanionic species. The iminium electrophiles are generated in situ from aldehydes, secondary amines, proton sponge, and silyl triflate. The reaction can be extended for introduction of chlorodifluoromethyl and iododifluoromethyl groups.
- Tsymbal, Artem V.,Kosobokov, Mikhail D.,Levin, Vitalij V.,Struchkova, Marina I.,Dilman, Alexander D.
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p. 7831 - 7835
(2015/03/18)
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- Deoxofluorination reactions using N,N-disubstituted aminodifluorosulfinium tetrafluoroborate salts
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The synthesis of N,N-disubstituted aminodifluorosulfinium tetrafluoroborate salts is reported, and their behavior as deoxofluorinating agent was evaluated. The deoxofluorination reactions were performed using a primary alcohol, a secondary alcohol and a ketone. Results show that subtle modification of the structure of the reagents can noticeably affect the reactivity and the selectivity in deoxofluorination reactions.
- Mahé, Olivier,L'Heureux, Alexandre,Couturier, Michel,Bennett, Christopher,Clayton, Simon,Tovell, David,Beaulieu, Francis,Paquin, Jean-Fran?ois
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- DISUBSTITUTED-AMINODIFLUOROSULFINIUM SALTS, PROCESS FOR PREPARING SAME AND METHOD OF USE AS DEOXOFLUORINATION REAGENTS
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The invention relates to disubstituted-aminodifluorosulfinium salts represented by the formula (I). Processes for preparing same and methods of use as deoxofluorinating reagent is also provided.
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Page/Page column 28
(2010/12/31)
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- Three-component coupling using arynes and aminosilanes for ortho-selective double functionalization of aromatic skeletons
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(Chemical Equation Presented) Arynes were found to couple with aminosilanes and carbonyl compounds in the presence of benzoic acid to provide 2-aminobenzhydrols. Sulfonylimines could also be applied to the reaction, enabling amino and aminomethyl moieties to be incorporated into contiguous positions of aromatic skeletons. Only a small amount of the three-component coupling product was obtained in the absence of benzoic acid, which confirms its vital role in the present reaction.
- Morishita, Takami,Fukushima, Hiroyuki,Yoshida, Hiroto,Ohshita, Joji,Kunai, Atsutaka
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p. 5452 - 5457
(2008/12/20)
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- A Simple and Highly Diastereoselective One-Pot Synthesis of Mannich-Bases
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A convenient one-pot procedure for the synthesis of β-amino ketones 5 from economical shelf reagents is described. Iminium salts 3 are generated in virtually quantitative yields from secondary amines 1 and aldehydes 2 mediated by NaI/Me3SiCl/NEt3. Subsequently, the salts 3 are used for the in situ aminoalkylation of enamines 4. The method provides the Mannich bases 5 in high yields and excellent diastereoselectivities (>96 % ds). It can also be applied for the aminoalkylation of other nucleophiles such as imines or electron-rich aromatic compounds.
- Arend, Michael,Risch, Nikolaus
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p. 974 - 976
(2007/10/03)
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- Synthesis of deoxydinucleoside phosphorodithioates
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The synthesis of a new class of DNA analogues called phosphorodithioate DNA is described. This analogue, which has a deoxynucleoside-OPS2O-deoxynucleoside internucleotide linkage, is isosteric and isopolar with the normal phosphodiester, inert toward nucleases, and potentially useful for a large number of biochemical and biological applications. Two methods are described for synthesizing this derivative. One route begins by condensing a deoxynucleoside phosphorodiamidite with a second appropriately protected deoxynucleoside to yield a deoxydinucleoside phosphoramidite. Sulfhydrolysis with H2S generates the H-phosphonothioate, which upon oxidation with sulfur yields the deoxydinucleoside phosphorodithioate. Alternatively, sequential treatment of the deoxydinucleoside phosphoramidite with a mercaptan and sulfur yields the deoxydinucleoside phosphorodithioate triester. These deoxydinucleotides in protected form can then be used to introduce the dithioate internucleotide linkage into DNA. The second route for generating dithioate DNA uses deoxynucleoside phosphorothioamidites. Two derivatives, the deoxynucleoside 3′-N,N-dimetnyl- or 3′-(N,N-tetramethylenephosphorothioamidite), were found to be especially attractive synthons as they could be prepared in stable form via a one-flask synthesis procedure and used to form the deoxydinucleoside thiophosphite rapidly (1-2 min with tetrazole as activator) in high yield. Subsequent oxidation with sulfur generates the completely protected phosphorodithioate linkage.
- Brill, Wolfgang K.-D.,Nielsen, John,Caruthers, Marvin H.
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p. 3972 - 3980
(2007/10/02)
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- A NEW SYNTHESIS OF AMIDES FROM ACYL FLUORIDES AND N-SILYLAMINES
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Amide bonds are formed readily under mild conditions by the reaction of N-silylamines with the hydrolytically stable acyl fluorides.
- Rajeswari, Sundaramoorthi,Jones, Robert J.,Cava, Michael P.
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p. 5099 - 5102
(2007/10/02)
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- Amination, III. Trimethylsilanol as Leaving Group, V. Silylation - Amination of Hydroxy N-Heterocycles
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Hydroxy N-heterocycles such as 18, 21, 26, and others are efficiently aminated in a one-step/one-pot procedure by silylation-amination to give 20, 23 - 25 etc.Silylation converts aromatic hydroxy N-heterocycles into activated and lipophilic intermediates of type 3, 8 which react in situ with ammonia, primary or secondary amines to form the corresponding mono-, bis- or tris-aminated products (5, 10).This addition-elimination of amines to O-silylated heterocycles is Lewis acid-catalysed and proceeds usually in high yields if the leaving group trimethylsilanol is converted in situ by excess silylated agent into hexamethyldisiloxane.Scope and limitations of this simple procedure are discussed.
- Vorbrueggen, Helmut,Krolikiewicz, Konrad
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p. 1523 - 1541
(2007/10/02)
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- SOLUTION SYNTHESIS OF FULLY PROTECTED THYMIDINE DIMERS USING VARIOUS PHOSPHORAMIDITES
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The synthesis of thymidine-3'-phosphoramidites of various amines and their use in the solution synthesis of fully protected thymidine dimers in high yields is desribed.
- Schwarz, Michael W.,Pfleiderer, Wolfgang
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p. 5513 - 5516
(2007/10/02)
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- A Simple Synthesis pf Primary Amines via their N,N-Bis(trimethylsilyl) Derivatives
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Primary halogen compounds 1 or the corresponding tosylates react with sodium bis(trimethylsilyl)amide (2) in hexamethyldisilazane to form N,N-bis(trimethylsilyl)amines 3, which are converted into the amine hydrochlorides 5 by treatment with aqueous HCl.
- Bestmann, Hans Juergen,Woelfel, Gerhard
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p. 1250 - 1254
(2007/10/02)
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