First Synthesis of a Mustard Oil Glucoside; The Enzymatic Lossen Rearrangement

Ettlinger, Martin G.; Lundeen, Allan J.

doi:10.1021/ja01564a066

Cited by 103 publications

(36 citation statements)

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“…The synthesis of phenylacetothiohydroxamate (PATH) was achieved by the method of Ettlinger and Lundeen (1957), also presented by Walter and Schaumann (1971). The product was crystallized as the organic acid in benzene/hexane, and the crystals were analyzed by 1 H-, 13 C-, 13 C DEPT-, and 2D ( 1 H and 13 C) COSY-NMR (data not shown).…”

Section: Chemical Synthesis Of Phenylacetothiohydroxamatementioning

confidence: 99%

Towards engineering glucosinolates into non-cruciferous plants

Geu‐Flores

Olsen

Halkier

2008

Planta

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Glucosinolates are amino acid-derived secondary metabolites present in cruciferous plants. Glucosinolates and their hydrolysis products are involved in defence against insects and pathogens, but are also known for their characteristic flavor and their cancer-preventive and antibacterial properties. This wide range of bioactivities has prompted a desire to engineer glucosinolates into non-cruciferous plants. We report the one-step transfer of the last three steps of the benzylglucosinolate pathway (comprising the C-S lyase, glycosyltransferase and sulfotransferase) from Arabidopsis to tobacco. This was achieved using an expression construct consisting of a single 2A polycistronic open reading frame, which allowed the expression of the three coding-sequences from a single promoter. When compared to wildtype plants, transgenic tobacco lines showed increased ability to convert the intermediate phenylacetothiohydroxamate to benzylglucosinolate upon in vivo feeding. Enzymatic assays using plant extracts demonstrated that the individual activities required for this conversion were enhanced in the transgenic plants. The relatively high conversion by wildtype plants in feeding assays supports the hypothesis that the last part of the glucosinolate pathway was recruited from existing detoxification reactions. Immunoblots confirmed that individual proteins were being successfully produced from the 2A polycistronic open reading frame, albeit fusion proteins could also be detected. In summary, we transferred the last three steps of the benzylglucosinolate pathway to tobacco as a first step towards engineering glucosinolates into non-cruciferous plants.

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Section: Chemical Synthesis Of Phenylacetothiohydroxamatementioning

confidence: 99%

Towards engineering glucosinolates into non-cruciferous plants

Geu‐Flores

Olsen

Halkier

2008

Planta

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“…In spite of the failure of this struct~lre to account for several of the observed reactions of the nlustard oil gluc~sides,~ it was accepted until 1936, when Ettlinger and Lundeen (6) pointed out that all the observed properties and reactions were consistent ivith the structure (II).4 New degradative evidence supported this structure, the correctness of which was conclusively established (7) by the synthesis of a conlpound with the structure (II)(R = C6HjCH2, X = (CH3)4N) which proved to be identical with the tetramethylanlrnoniu~n salt5 of the naturally occurring ~nustard oil glucoside, glucotropaeolin. Recently, in connection with certain biosynthetic and biochemical studies, we developed a new synthesis of the mustard oil glucosides, the key feature of which was the construction of the thiohydroximate skeleton by the addition of a thiol to a nitrile oxide (8).…”

Section: R-5=cmentioning

confidence: 96%

The Synthesis of Glucosinalbin and Glucoaubrietin

Benn¹

1965

Can. J. Chem.

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T h e first synthesis of the glucosinalbin and glucoaubrietin anions has been achieved b y sulfol~ation and deacetylation of the thiohydrosimates obtained by addition o f tctraacetylglucopyranosyl mercaptan to p-acctosyphenylacetonitrile oside and p-methoxypher~pl-acetonitrile oxide.The mustard oil glucosides form a group of natural coinpounds widely distributed through the plant kingdom and particularly common in the order Rhoeadales, especially within the families Cruciferae and Capparidaceae of this order (1). Eminent amongst these conlpounds is sinalbin, the glucosidic precursor of the mustard oil responsible for the well known flavor of white mustard, Sinupis alba L., a plant which has been used for medicinal and condinlental purposes for some 2.3 centuries (2).Sinalbin was first isolated from Sinapis alba in 1831 by Robiquet and B o~~t r o n (3). I11 1897 Gadanler (4) proposed the general structure (I) for the mustard oil glucosides, sinalbin being (I)(R = fi-I-IOC6H.,CH?, X = sinapinium cation).?In spite of the failure of this struct~lre to account for several of the observed reactions of the nlustard oil gluc~sides,~ it was accepted until 1936, when Ettlinger and Lundeen (6) pointed out that all the observed properties and reactions were consistent ivith the structure (II).4 New degradative evidence supported this structure, the correctness of which was conclusively established (7) by the synthesis of a conlpound with the structure (II)(R = C6HjCH2, X = (CH3)4N) which proved to be identical with the tetramethylanlrnoniu~n salt5 of the naturally occurring ~nustard oil glucoside, glucotropaeolin.

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“…The present status of myrosulfatase is doubtful because it has been shown that fission of the glycosidic bond by chemical means (59,60) or by thioglycosidase (105) is followed by a Lossen rearrangement with liberation of Sob2-ions. It may therefore be that myrosulfatase does not exist as such and its apparent action is simply a consequence of thioglycosidase activity.…”

Section: Myrosulfatasementioning

confidence: 99%

The Synthesis and Hydrolysis of Sulfate Esters

Ab¹

1960

Advances in Enzymology - And Related Areas of Molecular Biology

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First Synthesis of a Mustard Oil Glucoside; The Enzymatic Lossen Rearrangement

Cited by 103 publications

References 0 publications

Towards engineering glucosinolates into non-cruciferous plants

Towards engineering glucosinolates into non-cruciferous plants

The Synthesis of Glucosinalbin and Glucoaubrietin

The Synthesis and Hydrolysis of Sulfate Esters

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