- An efficient and atom-economical route to: N -aryl amino alcohols from primary amines
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In this paper we reported a novel method for generation of N-aryl amino alcohols from N,N-disubstituted picolinamides through reduction/ring-opening reaction with NaBH4. The N,N-disubstituted picolinamides can be easily obtained from primary am
- Xiao, Zhen,Li, Juanjuan,Yue, Qiang,Zhang, Qian,Li, Dong
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p. 34304 - 34308
(2018/10/24)
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- Ruthenium-Pincer-Catalyzed Hydrogenation of Lactams to Amino Alcohols
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By using the commercially available ruthenium pincer complex (Ru-MACHO-BH) as a catalyst, the challenging direct hydrogenation of lactams and analogues has been successfully accomplished to deliver corresponding value-added amino alcohols in good-to-excellent yields under mild reaction conditions. Remarkably, in addition to N-protected lactams, unprotected ones could also be readily reduced in the presence of a catalytic amount of weak base or even under neutral reaction conditions, which further highlights the broad substrate scope and the protocol efficiency.
- Chen, Jiangbo,Wang, Jiaquan,Tu, Tao
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p. 2559 - 2565
(2018/07/30)
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- Efficient nickel-catalysed: N -alkylation of amines with alcohols
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The selective N-alkylation of amines with alcohols via the borrowing hydrogen strategy represents a prominent sustainable catalytic method, which produces water as the only by-product and is ideally suited for the catalytic transformation of widely available alcohol reaction partners that can be derived from renewable resources. Intensive research has been devoted to the development of novel catalysts that are mainly based on expensive noble metals. However, the availability of homogeneous or heterogeneous non-precious metal catalysts for this transformation is very limited. Herein we present a highly active and remarkably easy-to-prepare Ni based catalyst system for the selective N-alkylation of amines with alcohols, that is in situ generated from Ni(COD)2 and KOH under ligand-free conditions. This novel method is very efficient for the functionalization of aniline and derivatives with a wide range of aromatic and aliphatic alcohols as well as diols and exhibits excellent functional group tolerance including halides, benzodioxane and heteroaromatic groups. Several TEM measurements combined with elemental analysis were conducted in order to gain insight into the nature of the active catalyst and factors influencing reactivity.
- Afanasenko, Anastasiia,Elangovan, Saravanakumar,Stuart, Marc C. A.,Bonura, Giuseppe,Frusteri, Francesco,Barta, Katalin
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p. 5498 - 5505
(2018/11/20)
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- Benzimidazolin-2-ylidene N-heterocyclic carbene complexes of ruthenium as a simple catalyst for the N-alkylation of amines using alcohols and diols
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Simple air and moisture stable ruthenium complexes 1-3 and 3a were synthesized from readily available benzannulated N-heterocyclic carbene ligands (bimy = benzimidazolin-2-ylidene). These complexes were found to be efficient catalysts for the alkylation of amines using alcohols as alkylating agents. Catalysts 1, 2 and 3a gave excellent yields of up to 99% for the alkylation of various amines using benzylic and aliphatic alcohols at 130 °C for 18 h under solventless conditions. Catalyst 3a bearing both phosphine and carbene ligands gave excellent yields of up to 98% for the synthesis of heterocyclic amines by double alkylation of primary amines using linear diols. The practical utility of these catalysts was demonstrated for the synthesis of pharmaceutically important amines in a more environmentally benign way under solventless conditions.
- Shan, Siah Pei,Xiaoke, Xie,Gnanaprakasam, Boopathy,Dang, Tuan Thanh,Ramalingam, Balamurugan,Huynh, Han Vinh,Seayad, Abdul Majeed
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p. 4434 - 4442
(2015/02/19)
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- Highly chemoselective reduction of amides (primary, secondary, tertiary) to alcohols using SmI2/amine/H2O under mild conditions
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Highly chemoselective direct reduction of primary, secondary, and tertiary amides to alcohols using SmI2/amine/H2O is reported. The reaction proceeds with C-N bond cleavage in the carbinolamine intermediate, shows excellent functional group tolerance, and delivers the alcohol products in very high yields. The expected C-O cleavage products are not formed under the reaction conditions. The observed reactivity is opposite to the electrophilicity of polar carbonyl groups resulting from the nX → πC=O (X = O, N) conjugation. Mechanistic studies suggest that coordination of Sm to the carbonyl and then to Lewis basic nitrogen in the tetrahedral intermediate facilitate electron transfer and control the selectivity of the C-N/C-O cleavage. Notably, the method provides direct access to acyl-type radicals from unactivated amides under mild electron transfer conditions.
- Szostak, Michal,Spain, Malcolm,Eberhart, Andrew J.,Procter, David J.
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supporting information
p. 2268 - 2271
(2014/03/21)
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- Iridium-catalyzed oxidant-free dehydrogenative C-H bond functionalization: Selective preparation of N-arylpiperidines through tandem hydrogen transfers
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Relay to the finish: The atom-economical tandem hydrogen autotransfer catalyzed by iridium(III) has been efficiently applied for the preparation of N-arylpiperidines starting from easily accessible anilines, diols, and aldehydes (see scheme). This protocol is also compatible with the use of diethyl carbonate as an ecofriendly solvent. Copyright
- Yuan, Kedong,Jiang, Fan,Sahli, Zeyneb,Achard, Mathieu,Roisnel, Thierry,Bruneau, Christian
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scheme or table
p. 8876 - 8880
(2012/10/08)
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- Catalytic hydrogenation of carboxamides and esters by well-defined Cp*Ru complexes bearing a protic amine ligand
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A novel catalytic method for the straightforward hydrogenation of carboxamides and esters to primary alcohols has been developed. Chiral modification in the ligand sphere of the well-defined Cp*Ru catalyst molecule opens up a new possibility for the development of an enantioselective hydrogenation of racemic substrates via dynamic kinetic resolution.
- Ito, Masato,Ootsuka, Takashi,Watari, Ryo,Shiibashi, Akira,Himizu, Akio,Ikariya, Takao
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supporting information; experimental part
p. 4240 - 4242
(2011/06/21)
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- A highly active catalyst for the hydrogenation of amides to alcohols and amines
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Amide-zing: The reaction between 2 equivalents of Ph2P(CH 2)2NH2 and cis-[Ru(CH3CN) 2(η3-C3H5)(cod)]BF4 (cod=1,5-cyclooctadiene) forms a highly active catalyst precursor for the selective hydrogenation of amides. The reaction proceeds with excellent atom economy, yield, and turnover numbers (TONs) under moderate reaction conditions. The technology offers a greener, practical approach to the use of metal hydride reagents commonly employed in both academia and industry. Copyright
- John, Jeremy M.,Bergens, Steven H.
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supporting information; experimental part
p. 10377 - 10380
(2011/12/04)
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- Dimethylzinc-initiated radical reaction of cyclic ethers with arylamines, alkoxyamines, and dialkylhydrazines
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Dimethylzinc-initiated radical reaction of THF with arylamines afforded aminoalcohols which were derived from the two molecules of THF and one molecule of an arylamine. The reaction seems to proceed via two-consecutive processes, electrophilic and then nucleophilic reactions of THF-derived species. Alkoxyamines and dialkylhydrazines reacted with electrophilic cyclic ether species to give the corresponding oximes and hydrazones of ω- hydroxyalkanal.
- Yamamoto, Yasutomo,Maekawa, Masaru,Akindele, Tito,Yamada, Ken-Ichi,Tomioka, Kiyoshi
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p. 379 - 384
(2007/10/03)
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- Ruthenium-complex-catalyzed N-(Cyclo)alkylation of aromatic amines with diols. Selective synthesis of N-(ω-hydroxyalkyl)anilines of type PhNH(CH2)(n)OH and of some bioactive arylpiperazines
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A new class of well-defined neutral mono-, and dicationic ruthenium(II) complexes containing a neutral terdentate donor system [C5H3N(CH2E)2- 2,6] (E = PPh2 (PNP) or NME2 (NN'N) has been found effective as catalyst precursor in N-(cyclo)alkylation reactions of aromatic amines with diols Y(CH2CH2OH)2 (Y = CH2, NR). With these catalysts, N-phenylpiperidine is synthesized from aniline and 1,5-pentanediol in 85% yield (at 180 °C for 24 h in 1.4-dioxane). With neutral RuCl2(NN'N)-(PPh3) as a catalyst precursor, aniline can be selectively N-monoalkylated with diols of the type HO(CH2)(n)OH (n = 4-6, 10) to give N-(n-hydroxyalkyl)anilines in 40-75 yield. To our knowledge, this represents the first useful catalytic route to this type of compounds. The new catalysts can also be used in the synthesis of arylpiperazines. For example, N-phenyl-N'-methylpiperazine is obtained from aniline and MeN(CH2CH2OH)2 in yields up to 34%. N- [m(Trifluoromethyl)phenyl]-N'-methylpiperazine, TFMPMP, is successfully produced from m-(trifluoromethyl)aniline and MeN-(CH2CH2OH)2 in 44% yield using monocationic [RuOTf(NN'N)(PPh3)]OTf as the catalyst precursor. A mechanism for the N-(cyclo)alkylation reaction is proposed.
- Abbenhuis,Boersma,Van Koten
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p. 4282 - 4290
(2007/10/03)
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- Photocleavage of the C-O bond of 9-phenanthrylmethyl ω-anilinoalkyl ethers via photo-induced intramolecular electron transfer
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Photoreactions of the title compounds nNHPh: Ar = 9-phenanthryl> 1 and 2 (n = 4 and 5) gave ω-alkan-1-ols 7 and 8 and ω-alkan-1-ols 9 and 10, respectively, by the cleavage of the C-O bond, while that of another title compound 3 (n = 6) gave spiro-compounds 17 and 18 with 12- and 14-membered-rings, respectively, as main products.The photoreaction is proposed to proceed via photo-induced intramolecular electron transfer from comparison of the reaction products with those in the photoreaction of ArCH2O3Ph 5 in the presence of N-methylaniline and acetic acid.The structures of spiro-compounds 17, 18, and the acetate of 9 were confirmed by X-ray crystal structure analysis.
- Sugimoto, Akira,Kimoto, Satoshi,Adachi, Tomohiro,Inoue, Hiroo
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p. 1459 - 1466
(2007/10/02)
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- Ruthenium Complex Catalyzed N-Heterocyclization. Syntheses of N-Substituted Piperidines, Morpholines, and Piperazines from Amines and 1,5-Diols
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1,5-Pentanediol reacts with aliphatic and aromatic primary amines in the presence of a ruthenium catalyst modified with phosphonic ligands to give N-substituted piperidines in fair to goods yields.The reactions were carried out at 150-180 deg C for 5 h in dioxane.The nature of the phosphorus ligands has a remarkable effect on the catalytic activity, For the reaction of aromatic amines, triphenylphosphine is effective, while for aliphatic amine more basic tributyl- or triethylphosphine is preferable.Amines also react with diethylene glycol and N-substituted diethanolamines in the presence of the ruthenium catalyst to give N-substituted morpholines and piperazines in good yields, respectively.
- Tsuji, Yasushi,Huh, Keun-Tae,Ohsugi, Yukihiro,Watanabe, Yoshihisa
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p. 1365 - 1370
(2007/10/02)
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