Abstract
A general pathway was devised to synthesize ω-methylsulfanylalkyl glucosinolates, which represent an important class of structurally homogeneous plant secondary metabolites. The required thiofunctionalized hydroximoyl chlorides were obtained from the corresponding α,ω-nitroalkyl methylsulfide precursors, involving as the key-step, a nitronate chlorination strategy. A coupling reaction with 1-thio-beta-d-glucopyranose, followed by O-sulfation of the intermediate thiohydroximate and final deprotection of the sugar moiety afforded the target compounds.
Highlights
Glucosinolates (GLs) 1 stand as molecular tags of the plant order Brassicales [1,2]
For most synthetic methods that have been developed for GLs over the years, the key step was the stereospecific formation of a thiohydroximate function, usually resulting from the 1,3-addition of a glucosyl mercaptan onto a transient nitrile oxide [15]
We report a general synthetic pathway to ω-methylsulfanylalkyl
Summary
Glucosinolates (GLs) 1 stand as molecular tags of the plant order Brassicales [1,2]. Those strikingly bio-relevant thiosaccharidic secondary metabolites are found without exception in all 17 families of this order. “Specialist” plants, which can be considered for convenient isolation of one specific GL in reasonable amount, are in very limited number [11,12,13] This is the case for thiofunctionalized GLs, for which the synthetic approach should be privileged to make available attractive substrates for biological studies [14,15]. For most synthetic methods that have been developed for GLs over the years, the key step was the stereospecific formation of a thiohydroximate function, usually resulting from the 1,3-addition of a glucosyl mercaptan onto a transient nitrile oxide [15] As they are generally unstable molecular species, nitrile oxides have to be generated in situ through base-induced conversion of hydroximoyl chlorides, (Figure 3), which in turn currently result from electrophilic chlorination of aldoximes [21]. Nitronate method vs. oxime method to access hydroximoyl chlorides [20]
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