Reactions of N-(o-carboxybenzoyl)-L-leucine: intramolecular catalysis of amide hydrolysis and imide formation by two carboxy groups

Onofrio, Alvaro B.; Gesser, José C.; Joussef, Antônio Carlos; Nome, Faruk

doi:10.1039/b007047p

Cited by 14 publications

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“…In a previous paper (Onofrio et al, 2001) we studied the intramolecular acid catalysis of N-(2-carboxybenzoyl)-lleucine methyl ester, (I), a simple model of aspartic proteinases which has been extensively investigated as a theoretical model (Wu et al, 2003a,b). The intramolecular reactions of (I) in aqueous solution result in both cyclization to form the imide N-phthaloylleucine, and hydrolysis of (I) to phthalic acid and leucine.…”

Section: Commentmentioning

confidence: 99%

N-(2-Carboxybenzoyl)-L-leucine methyl ester

et al. 2006

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The title compound (with the systematic name 2-{[(1S)-1-(methoxycarbonyl)-3-methylbutyl]aminocarbonyl}benzoic acid), C15H19NO5, crystallizes in the monoclinic space group P2(1), with two independent molecules per asymmetric unit. The most notable difference between the two molecules is in the dihedral angles between the planes of the carboxyl group and the benzene ring, which are 3.5 (3) and 25.7 (1) degrees . This difference may account for the fact that two competing reactions are observed in aqueous solution, namely cyclization to form the imide N-phthaloylleucine and hydrolysis of N-(2-carboxybenzoyl)-L-leucine methyl ester to phthalic acid and leucine.

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Section: Commentmentioning

confidence: 99%

N-(2-Carboxybenzoyl)-L-leucine methyl ester

et al. 2006

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“…Rapid ring opening gives then the anion of the corresponding carboxylic acid together with the alcohol. The mechanisms for the intramolecular cyclization of 2-(hydroxymethyl)benzoates [24], 2carbamoylbenzoates [27] [28] [55], or other related systems [25] [26] [29] [51] are very similar. However, in contrast to the 2-acylbenzoates, the internal nucleophile does not have to be generated by hydration.…”

Section: Rate Constants For the Alkaline Hydrolysis By Neighboring-grmentioning

confidence: 99%

Controlled Release of Perfumery Alcohols by Neighboring‐Group Participation. Comparison of the Rate Constants for the Alkaline Hydrolysis of 2‐Acyl‐, 2‐(Hydroxymethyl)‐, and 2‐Carbamoylbenzoates

Laumer

Frérot

Herrmann

2003

Helvetica Chimica Acta

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Dedicated to our colleague Dr. Sina Escher on the occasion of her retirement A series of 2-acylbenzoates 1 and 2, 2-(hydroxymethyl)benzoates 3, 2-carbamoylbenzoates 4 ± 6, as well as the carbamoyl esters 7 or 8 of maleate or succinate, respectively (see Fig. 2), were prepared in a few reaction steps, and the potential use of these compounds as chemical delivery systems for the controlled release of primary, secondary, and tertiary fragrance alcohols was investigated. The rate constants for the neighboringgroup-assisted alkaline ester hydrolysis were determined by anal. HPLC in buffered H 2 O/MeCN solution at different pH ( Table 1). The rates of hydrolysis were found to depend on the structure of the alcohol, together with the precursor skeleton and the structure of the neighboring nucleophile that attacks the ester function. Primary alcohols were released more rapidly than secondary and tertiary alcohols, and benzoates of allylic primary alcohols (e.g., geraniol) were hydrolyzed 2 ± 4 times faster than their homologous saturated alcohols (e.g., citronellol). For the same leaving alcohol, 2-[(ethylamino)carbonyl]benzoates cyclized faster than the corresponding 2-(hydroxymethyl)benzoates, and much faster than their 2-formyl and 2-acetyl analogues (see, e.g., Fig. 4). Within the carbamoyl ester series, 2-[(ethylamino)carbonyl]benzoates were found to have the highest rate constants for the alkaline ester hydrolysis, followed by unsubstituted 2-(aminocarbonyl)benzoates, or the corresponding isopropyl derivatives. To rationalize the influence of the different structural changes on the hydrolysis kinetics, the experimental data obtained for the 2-[(alkylamino)carbonyl]benzoates were compared with the results of density-functional computer simulations ( Table 2 and Scheme 4). Based on a preliminary semi-empirical conformation analysis, density-functional calculations at the B3LYP/6-31G** level were carried out for the starting precursor molecules, several reaction intermediates, and the cyclized phthalimides. For the same precursor skeleton, these simple calculations were found to model the experimental data correctly. With an understanding of the influence of structural parameters on the rate constants obtained in this work, it is now possible to influence the rates of hydrolysis over several orders of magnitude, to design tailor-made precursors for a large variety of fragrance alcohols, and to predict their efficiency as controlled-release systems in practical applications.

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“…The intramolecular reactions of N-(o-carboxybenzoyl)--leucine 111 were studied in aqueous solution, as a function of the hydrogen ion concentration. 46 Two competing reactions were observed: i) cyclization to form the imide N-phthaloylleucine 112, and ii) hydrolysis of 111 to phthalic acid 113 and leucine 114 (Scheme 32). Individual rate constants for cyclization and hydrolysis were obtained from the overall rate constants and product distributions.…”

Section: Scheme 25 Scheme 26mentioning

confidence: 99%

6 Reaction mechanisms : Part (i) Polar reactions

Dalby

2002

Annu. Rep. Prog. Chem., Sect. B: Org. Chem.

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Reactions of N-(o-carboxybenzoyl)-L-leucine: intramolecular catalysis of amide hydrolysis and imide formation by two carboxy groups

Cited by 14 publications

References 14 publications

N-(2-Carboxybenzoyl)-L-leucine methyl ester

N-(2-Carboxybenzoyl)-L-leucine methyl ester

Controlled Release of Perfumery Alcohols by Neighboring‐Group Participation. Comparison of the Rate Constants for the Alkaline Hydrolysis of 2‐Acyl‐, 2‐(Hydroxymethyl)‐, and 2‐Carbamoylbenzoates

6 Reaction mechanisms : Part (i) Polar reactions

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