o-(α-l-rhamnopyranosyloxy)benzylamine and o-hydroxybenzylamine in Reseda odorata

doi:10.1016/S0031-9422(00)85194-8

Phytochemistry

Volume 9, Issue 4, April 1970, Pages 865-870

https://doi.org/10.1016/S0031-9422(00)85194-8 Get rights and content

Abstract

Two new natural products, o-(α-l-rhamnopyranosyloxy)benzylamine and o-hydroxybenzylamine, have been isolated from flowers of Reseda odorata L. The proposed structures have been confirmed by transformation of the rhamnoside into N-[o-(O-triacetyl-α-l-rhamnopyranosyloxy)benzyl]acetamide and by synthesis of this amide and the two amines. A possible biogenetic relationship between the amines and glucosinolates is briefly discussed.

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Cited by (19)

Investigation of glucosinolates in the desert plant Ochradenus baccatus (Brassicales: Resedaceae). Unveiling glucoochradenin, a new arabinosylated glucosinolate
2021, Phytochemistry
Citation Excerpt :
Compound 3a was previously reported as 2″-O-(α-L-rhamnopyranosyloxy)benzylglucosinolate, from the genus Reseda (Resedaceae) (Olsen and Sørensen, 1979). Another example of a rhamnosylated form of benzylic GSL was identified in Moringa oleifera (Moringaceae), where the rhamnose is connected to the para position (Daxenbichler et al., 1991; Gueyrard et al., 2000; Kjaer and Malver, 1979; Sørensen 1970). Six GSLs were identified - via isolation and structural elucidation of desulfated derivatives - from the roots of O. baccatus, a member of the Resedaceae family, and a distant relative of the Brassicaceae.
Here we describe the structure elucidation and quantification of six glucosinolates (GSLs) from the roots of the desert plant Ochradenus baccatus, Delile 1813 (family Resedaceae; order Brassicales). The structure elucidation was established on the corresponding enzymatically desulfated derivatives of the native GSLs of the plant. Among these GSLs we describe the previously undescribed 2″-O-(α-L-arabinopyranosyloxy)benzylglucosinolate (1a), for which we propose the name glucoochradenin. The other five glucosinolates (2a-6a) were (2S)-2-hydroxy-2-phenylethylglucosinolate (2a; glucobarbarin), 2″-O-(α-L-rhamnopyranosyloxy)benzylglucosinolate (3a), benzylglucosinolate (4a; glucotropaeolin), indol-3-ylmethylglucosinolate (5a; glucobrassicin) and phenethylglucosinolate (6a; gluconasturtiin), all elucidated as their desulfo-derivatives, 2b-6b respectively). Structures were elucidated by MS and 1D and 2D-NMR techniques, the identity of the arabinose verified by ion chromatography, and the absolute configuration of the sugar units determined by hydrolysis, coupling to cysteine methyl-ester and phenyl isothiocyanate followed by HPLC-MS analysis of the resulted diastereomers. Response factors were generated for desulfo-2″-O-(α-L-arabinopyranosyloxy)benzylglucosinolate and for desulfo-2″-O-(α-L-rhamnopyranosyloxy)benzylglucosinolate and all six GSLs were quantified, indicating that the root of O. baccatus is rich in GSLs (Avg. 61.3 ± 10.0 μmol/g DW and up to 337.2 μmol/g DW).
Glucosinolate structures in evolution
2012, Phytochemistry
Citation Excerpt :
The first data suggesting in planta GSL turnover were of a structural nature. Several authors reported structurally similar GSLs and amines in various plants, e.g. 4-hydroxybenzyl amine and 4-hydroxybenzylGSL in Sinapis alba (Larsen, 1965) and 2-(α-l-rhamnopyranosyloxy)benzyl amine and the corresponding 2-(α-l-rhamnopyranosyloxy)benzylGSL in Reseda odorata (Sørensen, 1970; Olsen and Sørensen 1979). As the position of the C-N bond in these amines corresponds to the position in isothiocyanates but not in nitriles or GSLs, this observation would suggest that isothiocyanates formed in vivo are converted into amines.
By 2000, around 106 natural glucosinolates (GSLs) were probably documented. In the past decade, 26 additional natural GSL structures have been elucidated and documented. Hence, the total number of documented GSLs from nature by 2011 can be estimated to around 132. A considerable number of additional suggested structures are concluded not to be sufficiently documented. In many cases, NMR spectroscopy would have provided the missing structural information. Of the GSLs documented in the past decade, several are of previously unexpected structures and occur at considerable levels. Most originate from just four species: Barbarea vulgaris, Arabidopsis thaliana, Eruca sativa and Isatis tinctoria. Acyl derivatives of known GSLs comprised 15 of the 26 newly documented structures, while the remaining exhibited new substitution patterns or chain length, or contained a mercapto group or related thio-functionality.
GSL identification methods are reviewed, and the importance of using authentic references and structure-sensitive detection methods such as MS and NMR is stressed, especially when species with relatively unknown chemistry are analyzed. An example of qualitative GSL analysis is presented with experimental details (group separation and HPLC of both intact and desulfated GSLs, detection and structure determination by UV, MS, NMR and susceptibility to myrosinase) with emphasis on the use of NMR for structure elucidation of even minor GSLs and GSL hydrolysis products. The example includes identification of a novel GSL, (R)-2-hydroxy-2-(3-hydroxyphenyl)ethylglucosinolate.
Recent investigations of GSL evolution, based on investigations of species with well established phylogeny, are reviewed. From the relatively few such investigations, it is already clear that GSL profiles are regularly subject to evolution. This result is compatible with natural selection for specific GSL side chains. The probable existence of structure-specific GSL catabolism in intact plants suggests that biochemical evolution of GSLs has more complex implications than the mere liberation of a different hydrolysis product upon tissue disruption.
The enzymic and chemically induced decomposition of glucosinolates
2006, Phytochemistry
While the myrosinase–glucosinolate system has been reviewed in recent years by a number of authors, little attention has been paid to the enzymic and non-enzymic degradation of glucosinolates. Non-enzymic degradation processes are particularly important in the processing of brassica vegetables with respect to both flavour and in the role of glucosinolates as precursors of anticancer compounds in the diet. This review highlights early empirical work on glucosinolate degradation along with more recent aspects related to current research on mechanism of glucosinolate degradation in plants, microbes and animals.
The chemical diversity and distribution of glucosinolates and isothiocyanates among plants
2001, Phytochemistry
Glucosinolates (β-thioglucoside-N-hydroxysulfates), the precursors of isothiocyanates, are present in sixteen families of dicotyledonous angiosperms including a large number of edible species. At least 120 different glucosinolates have been identified in these plants, although closely related taxonomic groups typically contain only a small number of such compounds. Glucosinolates and/or their breakdown products have long been known for their fungicidal, bacteriocidal, nematocidal and allelopathic properties and have recently attracted intense research interest because of their cancer chemoprotective attributes. Numerous reviews have addressed the occurrence of glucosinolates in vegetables, primarily the family Brassicaceae (syn. Cruciferae; including Brassica spp and Raphanus spp). The major focus of much previous research has been on the negative aspects of these compounds because of the prevalence of certain “antinutritional” or goitrogenic glucosinolates in the protein-rich defatted meal from widely grown oilseed crops and in some domesticated vegetable crops. There is, however, an opposite and positive side of this picture represented by the therapeutic and prophylactic properties of other “nutritional” or “functional” glucosinolates. This review addresses the complex array of these biologically active and chemically diverse compounds many of which have been identified during the past three decades in other families. In addition to the Brassica vegetables, these glucosinolates have been found in hundreds of species, many of which are edible or could provide substantial quantities of glucosinolates for isolation, for biological evaluation, and potential application as chemoprotective or other dietary or pharmacological agents.
Glucosinolates in Sesamoides canescens and S. pygmaea: Identification of 2-(α-l-arabinopyranosyloxy)-2-phenylethylglucosinolate
1981, Phytochemistry
A new natural product, 2-(α-l-arabinopyranosyloxy)-2-phenylethylglucosinolate, has been isolated from Sesamoides canescens. This glucosinolate together with 2-hydroxy-2-phenylethylglucosinolate and 2-phenetliylglucosinolate in a 1:1:1 ratio constitutes about 90 % of the total glucosinolate pool in green parts of the plant. Phenethylglucosinolate constitutes about 70 % of the total glucosinolate pool in green parts of S. pygmaea together with minor amounts of the two other glucosinolates. In addition, both plants contain at least seven other glucosinolates. The structure of the new natural product has been confirmed by transformations into d-glucose, l-arabinose, N-(2-(α-l-arabinopyranosyloxy)-2-phenylethyl)thiourea, 3-(α-l-arabinopyranosyloxy)-3-phenylpropionitrile and 3-hydroxy-3-phenylpropionic acid, respectively. The significance of this investigation is briefly discussed in relation to the methods used in glucosinolate analysis, chemotaxonomy and possible catabolic transformation of glucosinolates into amines.
Insulin-like, and insulin-antagonistic, carbohydrate derivatives. The synthesis of aryl and aralkyl d-mannopyranosides and 1-thio-d-mannopyranosides
1980, Carbohydrate Research
A number of novel, aryl and aralkyl d-mannopyranosides and 1-thio-d-mannopyranosides were synthesized for evaluation of insulin-like and insulin-antagonistic properties. The substituted-phenyl α-d-mannopyranosides were prepared by the general procedure of Helferich and Schmitz-Hillebrecht, the substituted-phenyl 1-thio-α-d-mannopyranosides by a method corresponding to the Michael synthesis of aromatic glycosides, and the aralkyl 1-thio-α-d-mannopyranosides by aralkylation of 2,3,4,6-tetra-O-acetyl-1-thio-α-d-mannopyranose (15) and subsequent O-deacetylation. Compound 15 was obtained by basic cleavage of the amidino group in 2-S-(tetra-O-acetyl-α-d-mannopyranosyl)-2-thiopseudourea hydrobromide, the product of the reaction of tetra-O-acetyl-α-d-mannosyl bromide with thiourea. Benzyl 1-thio-β-d-mannopyranoside, obtained by reaction of the sodium salt of 1-thio-β-d-mannopyranose with α-bromotoluene, and benzyl 1-thio-α-l-mannopyranoside were also synthesized, in order to assess the stereospecificity of the biological activities measured.

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o-(α-l-rhamnopyranosyloxy)benzylamine and o-hydroxybenzylamine in Reseda odorata

Abstract

Biochim. Biophys. Acta

Tetrahedron Letters

J. Org. Chem.

Acta Chem. Scand.

Acta Chem. Scand.

Biochim. Biophys. Acta

Bull. Chem. Soc. Japan

Dissertation Abstr.

J. Chem. Soc. Japan Ind. Chem. Sect.

Chem. Abs.