- Synthesis of secondary and tertiary amides without coupling agents from amines and potassium acyltrifluoroborates (KATs)
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Although highly effective for most amide syntheses, the activation of carboxylic acids requires the use of problematic coupling reagents and is often poorly suited for challenging cases such as N-methyl amino acids. As an alternative to both secondary and tertiary amides, we report their convenient synthesis by the rapid oxidation of trifluoroborate iminiums (TIMs). TIMs are easily prepared by acid-promoted condensation of potassium acyltrifluoroborates (KATs) and amines and are cleanly and rapidly oxidized to amides with hydrogen peroxide. The overall transformation can be conducted either as a one-pot procedure or via isolation of the TIM. The unique nature of the neutral, zwitterionic TIMs makes possible the preparation of tertiary amides via an iminium species that would not be accessible from other carbonyl derivatives and can be conducted in the presence of unprotected functional groups including acids, alcohols and thioethers. In preliminary studies, this approach was applied to the late-stage modifications of long peptides and the iterative synthesis of short, N-methylated peptides without the need for coupling agents.
- Bode, Jeffrey W.,Ryan, Sarah J.,Schuhmacher, Anne,Shiro, Tomoya
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p. 7609 - 7614
(2020/08/14)
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- Amidation of unactivated ester derivatives mediated by trifluoroethanol
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A catalytic amidation protocol mediated by 2,2,2-trifluoroethanol has been developed, facilitating the condensation of unactivated esters and amines, furnishing both secondary and tertiary amides. The complete scope and limitations of the method are described, along with modified conditions for challenging substrates such as acyclic secondary amines and chiral esters with retention of chiral integrity.
- McPherson, Christopher G.,Caldwell, Nicola,Jamieson, Craig,Simpson, Iain,Watson, Allan J. B.
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p. 3507 - 3518
(2017/04/26)
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- Design and synthesis of ruthenium(II) OCO pincer type NHC complexes and their catalytic role towards the synthesis of amides
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The present contribution describes the synthesis and characterization of a family of robust ruthenium complexes, supported by a tridentate pincer ligand of the type bis-phenolate-N-heterocyclic carbene [ tBu(OCO) 2-] (NHC). Ruthenium(II) complexes (1-3) bearing bis-phenolate-N-heterocyclic carbene ligand were synthesized in good yields by the reaction of imidazolinium proligand (HL) with metal precursors [RuHCl(CO)(EPh3)2(B)] (E = P or As; B = PPh3, AsPh3 or Py) by transmetalation from the corresponding silver carbene complex. All the Ru(II)-NHC complexes have been characterized by elemental analyses, spectroscopic methods as well as ESI mass spectrometry. Based on the spectral results, an octahedral geometry was assigned for all the complexes. The tridentate nature of the tBu(OCO) 2- ligand as well as some level of steric protection provided by the t Bu groups may rationalize the excellent stability of the Ru-Ccarbene bond in the present systems. Moreover, for the explorations of catalytic potential of the synthesized compounds, all the three [Ru-NHC] complexes (1-3) were tested as catalysts for amidation of alcohols with amines. Notably, the complex 1 was found to be very efficient and versatile catalyst towards amidation of a wide range of alcohols with amines. [Figure not available: see fulltext.].
- Nirmala, Muthukumaran,Viswanathamurthi, Periasamy
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- Synthesis and characterization of bridged bis(amidato) rare earth metal amides and their applications in C-N bond formation reactions
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Based on three bisamide proligands H2Ln (n = 1-3) (H2L1 = [(Me3C6H2CONHCH2)2CH2], H2L2 = [(Me3C6H2CONHCH2)2C(CH3)2], H2L3 = [Me3C6H2CONH(CH2)2]2NCH3), eight bis(amidato) trivalent rare-earth metal amides {LnRE[N(TMS)2]}2 (n = 1, RE = La (1), Sm (2), Nd (3), Y (4); n = 2, RE = La (5), Nd (6); n = 3, RE = La (7), Nd (8); TMS = SiMe3) were successfully synthesized by treatment of H2Ln with RE[N(TMS)2]3 in a 1:1 molar ratio. Complexes 3, and 5-8 were characterized by single-crystal X-ray diffraction, and NMR characterization was carried out for the La complexes 1, 5, 7 and the Y complex 4. These complexes exhibited high catalytic activities in both the direct amidation of aldehydes and the addition of amines with carbodiimine. It was found that the bis(amidato) rare earth metal amides bearing different linkers have different effects on the transformations and lanthanum and neodymium complexes performed better than others.
- Zhao, Bei,Xiao, Yang,Yuan, Dan,Lu, Chengrong,Yao, Yingming
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p. 3880 - 3887
(2016/03/05)
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- Anionic phenoxy-amido rare-earth complexes as efficient catalysts for amidation of aldehydes with amines
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A series of anionic organo-rare-earth amido complexes stabilized by dianionic phenoxy-amido ligands were prepared and their catalytic behavior for amidation reactions of aldehydes with amines was elucidated. Amine elimination reaction of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with an equimolar of lithium aminophenoxy {[HNO]1Li(THF)}2, which was prepared by the reaction of [HNOH]1 {[HNOH]1 = N-p-fluoro-phenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine} with one equivalent of n-BuLi in tetrahydrofuran (THF) in situ, gave the anionic phenoxy-amido rare earth amido complexes [NO]12Ln[N(SiMe3)2][Li(THF)]2 [Ln = Y (1), Yb (2), Sm (3), Nd (4)] in high isolated yields. Similar reactions of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with {[HNO]2Li(THF)}2, and {[HNO]3Li(THF)}2 in THF gave the anionic rare-earth amides [NO]22Ln[N(SiMe3)2][Li(THF)]2 [Ln = Sm (5), Nd (6)] and [NO]32Ln[N(SiMe3)2][Li(THF)]2 [Ln = Sm (7), Nd (8)] {[HNOH]2 = N-p-chloro-phenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine; [HNOH]3 = N-p-bromo-phenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine}, respectively. All of these complexes were fully characterized. X-ray structural determination revealed that these complexes are isostructural, and have solvated monomeric structures. Each of the rare-earth ions is coordinated by two phenoxy-amido ligands and one N(SiMe3)2 group, and the coordination geometry can be described as a distorted trigonal bipyramid. Each of the lithium atoms is surrounded by one aryloxo group, one amido group and one THF molecule, and the coordination geometry can be described as a trigonal plane. The catalytic behavior of these rare-earth amides for the amidation reaction of aldehyde with amine was elucidated. It was found that these complexes are efficient catalysts for this transformation to produce amides in good to excellent yields under mild reaction conditions, and in some cases, diacylamide compounds can be prepared conveniently.
- Wang, Chao,Huang, Lingling,Lu, Min,Zhao, Bei,Wang, Yaorong,Zhang, Yong,Shen, Qi,Yao, Yingming
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p. 94768 - 94775
(2015/11/24)
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- N-heterocyclic carbene based ruthenium-catalyzed direct amide synthesis from alcohols and secondary amines: Involvement of esters
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A well-defined N-heterocyclic carbene based ruthenium complex was developed as a highly active precatalyst for the direct amide synthesis from alcohols and secondary amines. Notably, reaction of 1-hexanol and dibenzylamine afforded 60% of the corresponding amide using our catalytic system, while no amide formation was observed for this reaction with the previously reported catalytic systems. Unlike the previously reported amidation with less sterically hindered alcohols and amines, involvement of ester intermediates was observed (Figure presented).
- Chen, Cheng,Zhang, Yao,Hong, Soon Hyeok
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experimental part
p. 10005 - 10010
(2012/02/05)
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- Synthesis and structural diversity of heterobimetallic lanthanide-potassium complexes and catalytic activity for amidation of aldehydes with amines
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Four heterobimetallic lanthanide-potassium complexes stabilized by the carbon-bridged bis(phenolate) ligand MBMP2- (MBMP = 2,2′-methylene bis(6-tert-butyl-4-methylphenolate)), [{(MBMP) 2La(THF)2}2K][K(THF)6] (1), [(MBMP)Nd(μ-MBMP)K(THF)]2 (2), [(THF)2Sm(MBMP) 2K(THF)2] (3), and [(THF)2Yb(MBMP) 2K(THF)3] (4), were synthesized, and their structural features were provided. It was found that the ionic radii of lanthanide metals have a profound effect on the structures of the heterobimetallic complexes. Complexes 1 to 4 are efficient catalysts for amidation reactions of aldehydes with amines to produce amides in good to excellent yields under mild conditions.
- Xu, Bin,Huang, Lingling,Yang, Zijian,Yao, Yingming,Zhang, Yong,Shen, Qi
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experimental part
p. 3588 - 3595
(2011/09/12)
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- Anionic bridged bis(amidinate) lithium lanthanide complexes: Efficient bimetallic catalysts for mild amidation of aldehydes with amines
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Anionic bridged bis(amidinate) lithium lanthanide complexes have been found to be efficient catalysts for the amidation of aldehydes with amines under mild conditions. The activity follows the order : yttrium neodymium europium ytterbium. The catalysts are available for the formation of benzamides derived from pyrrolidine, piperidine, and morpholine with good to excellent yields. In comparison with the corresponding neutral complexes, the anionic complexes show higher activity and a wider range of scope for the amines. A cooperation of the lanthanide and lithium metals in this process is proposed to contribute to the high activity of the present catalyst.
- Wang, Junfeng,Li, Junmei,Xu, Fan,Shen, Qi
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supporting information; experimental part
p. 1363 - 1370
(2009/12/09)
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- Heterobimetallic lanthanide/sodium phenoxides: Efficient catalysts for amidation of aldehydes with amines
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Heterobimetallic lanthanide/sodium phenoxides were found to be efficient catalysts for amidation of aldehydes with amines under mild conditions. The reactivity follows the order Nd 2C6H3O iPr) 2C6H3O 2C 6H3O for phenoxide groups. In comparison with the corresponding monometallic complexes, heterobimetallic complexes show higher activity and a wider range of scope of amines. A cooperation of lanthanide and sodium in this process is proposed to contribute to the high activity of the present catalyst.
- Li, Junmei,Xu, Fan,Zhang, Yong,Shen, Qi
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supporting information; experimental part
p. 2575 - 2577
(2009/07/18)
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