Simple One-Flask Method for the Preparation of Hydroxamic Acids

Giacomelli, Giampaolo; Porcheddu, Andrea; Salaris, Margherita

doi:10.1021/ol034903j

Cited by 91 publications

(53 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[17] Under these conditions, the reaction of 1 with O-benzyl-hydroxylamine resulted in the isolation of 2 in good yields (Scheme 4, procedure a). A further improvement in the reaction of 1 to 2 was achieved by using ethylchloroformiate as activating agent (Scheme 4, procedure b).…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Solution Thermodynamics, and X‐ray Study of Cu^II [12]Metallacrown‐4 with GABA Hydroxamic Acid: An Unprecedented Crystal Structure of a [12]MC‐4 with a γ‐Aminohydroxamate

Tegoni

Ferretti

Sansone

et al. 2007

Chemistry A European J

View full text Add to dashboard Cite

The solution equilibria of gamma-aminobutanehydroxamic acid (GABAha) with H+ and Cu2+ were investigated by potentiometry, titration calorimetry, spectrophotometry, NMR spectroscopy, and ESI-MS. The thermodynamic parameters of the CuII [12]metallacrown-4 obtained for GABAha were compared with those of the corresponding complexes of (S)-alpha-Alaha and beta-Alaha. The stability (-DeltaG0) sequence was beta-Alaha>>alpha-Alaha>GABAha, whereas the order of formation enthalpies (-DeltaH0) was beta-Alaha>>GABAha>alpha-Alaha. These data were interpreted on the basis of the dimensions of the chelate rings and the planarity of the metallamacrocycles. The CuII [12]metallacrown-4 ([12]MC-4) complex of GABAha was isolated and its crystal structure, which is the first reported for a [12]MC-4 of a gamma-aminohydroxamic acid, fully supports the structural features interpreted from the thermodynamic data.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthesis, Solution Thermodynamics, and X‐ray Study of Cu^II [12]Metallacrown‐4 with GABA Hydroxamic Acid: An Unprecedented Crystal Structure of a [12]MC‐4 with a γ‐Aminohydroxamate

Tegoni

Ferretti

Sansone

et al. 2007

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Compounds 1-12 have been reported elsewhere [31][32][33][34][35][36][37][38][39][40][41][42] using different procedures to those described here.…”

Section: Hydroxamic Acid Synthesesmentioning

confidence: 99%

An Experimental and Computational Approach to Understanding the Reactions of Acyl Nitroso Compounds in [4 + 2] Cycloadditions

et al. 2015

View full text Add to dashboard Cite

. (2015) 'An experimental and computational approach to understanding the reactions of acyl nitroso compounds in[4+2]-cycloadditions.', Journal of organic chemistry., 80 (19). pp. 9518-9534. Further information on publisher's website:http://dx.doi.org/10.1021/acs.joc.5b01470Publisher's copyright statement:This document is the Accepted Manuscript version of a Published Work that appeared in nal form in The Journal of Organic Chemistry, copyright c American Chemical Society after peer review and technical editing by the publisher. To access the nal edited and published work see http://dx.doi.org/10.1021/acs.joc.5b01470. Additional information:Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-pro t purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. AbstractCatalytic aerobic oxidation of phenyl hydroxycarbamate 1 and 1-hydroxy-3-phenylurea 2 using CuCl 2 and 2-ethyl-2-oxazoline in methanol gave acyl nitroso species in situ, which were trapped in nitrosoDiels-Alder (NDA) reactions with various dienes to afford the corresponding cycloadducts in high yields (90-98%). Competing ene products were also present for dienes containing both alkene π-bonds and allylic σ-bonds, and the ene yields are higher with 1 than with 2. The use of the chiral hydroxamic acid, (R)-1-hydroxy-3-(1-phenylethylurea) 3 (same conditions) gave NDA cycloadducts in high yields (97-99%) with no ene product from 2,3-dimethyl-1,3-butadiene. NDA cycloadducts were not obtained from other hydroxamic acid analogues [RCONHOH (R = PhCH 2 4; Ph(CH 2 ) 2 5; Ph(CH 2 ) 3 6; Ph(CH 2 ) 4 7; Ph 8; 2-pyridyl 9; 3-pyridyl 10], with various dienes using the copper-oxidation, but were obtained using sodium periodate, resulting in variable NDA yields (13-51%) from hydroxamic acids 1-10 with cyclohexa-1,3-diene and 2,3-dimethyl-1,3-butadiene (several cycloadducts characterized by X-ray crystallography). The NDA and nitroso-ene reaction pathways of nitroso intermediates with dienes were mapped by DFT computations (B3LYP/6-31G*) which showed that the acyl nitroso species are super-2 reactive and activation energies in the NDA processes are lower than the isomerization barriers between some cis-and trans-butadienes.

show abstract

“…[46] Variations of these methods have been reported and are summarised in a recent paper that describes a simple onepot method for the syntheses of hydroxamic acids in high yields. [47] The formation of hydroxamic acids and bioactive hydroxamate-containing compounds in both solution and solid phase has also recently been the subject of a comprehensive review by Lou et al [48] Two possible hydroxamic acid tautomers exist ( Figure 5); the keto tautomer, which is predominant under acidic conditions, and the enol form, which is more stable in alkaline media. [49] Furthermore, NMR spectroscopic studies have shown that each tautomer can exist as (E) and (Z) isomers ( Figure 5), further extending their structural diversity.…”

Section: Syntheses and Structuresmentioning

confidence: 99%

Hydroxamic Acids − An Intriguing Family of Enzyme Inhibitors and Biomedical Ligands

2004

View full text Add to dashboard Cite

show abstract

Simple One-Flask Method for the Preparation of Hydroxamic Acids

Abstract: [reaction: see text] A one-step conversion of carboxylic acids to hydroxamic acids under very mild conditions is described. This simple and efficient method has been applied for the synthesis of enantiopure hydroxamate of alpha-amino acids and peptides.

Cited by 91 publications

References 39 publications

Synthesis, Solution Thermodynamics, and X‐ray Study of Cu^II [12]Metallacrown‐4 with GABA Hydroxamic Acid: An Unprecedented Crystal Structure of a [12]MC‐4 with a γ‐Aminohydroxamate

Synthesis, Solution Thermodynamics, and X‐ray Study of Cu^II [12]Metallacrown‐4 with GABA Hydroxamic Acid: An Unprecedented Crystal Structure of a [12]MC‐4 with a γ‐Aminohydroxamate

An Experimental and Computational Approach to Understanding the Reactions of Acyl Nitroso Compounds in [4 + 2] Cycloadditions

Hydroxamic Acids − An Intriguing Family of Enzyme Inhibitors and Biomedical Ligands

Contact Info

Product

Resources

About

Simple One-Flask Method for the Preparation of Hydroxamic Acids

Abstract: [reaction: see text] A one-step conversion of carboxylic acids to hydroxamic acids under very mild conditions is described. This simple and efficient method has been applied for the synthesis of enantiopure hydroxamate of alpha-amino acids and peptides.

Cited by 91 publications

References 39 publications

Synthesis, Solution Thermodynamics, and X‐ray Study of CuII [12]Metallacrown‐4 with GABA Hydroxamic Acid: An Unprecedented Crystal Structure of a [12]MC‐4 with a γ‐Aminohydroxamate

Synthesis, Solution Thermodynamics, and X‐ray Study of CuII [12]Metallacrown‐4 with GABA Hydroxamic Acid: An Unprecedented Crystal Structure of a [12]MC‐4 with a γ‐Aminohydroxamate

An Experimental and Computational Approach to Understanding the Reactions of Acyl Nitroso Compounds in [4 + 2] Cycloadditions

Hydroxamic Acids − An Intriguing Family of Enzyme Inhibitors and Biomedical Ligands

Contact Info

Product

Resources

About

Synthesis, Solution Thermodynamics, and X‐ray Study of Cu^II [12]Metallacrown‐4 with GABA Hydroxamic Acid: An Unprecedented Crystal Structure of a [12]MC‐4 with a γ‐Aminohydroxamate

Synthesis, Solution Thermodynamics, and X‐ray Study of Cu^II [12]Metallacrown‐4 with GABA Hydroxamic Acid: An Unprecedented Crystal Structure of a [12]MC‐4 with a γ‐Aminohydroxamate