A highly enantioselective tandem Michael addition of tryptamine-derived oxindoles to alkynones was developed by taking advantage of a chiral N,N'-dioxide Sc(OTf) catalyst. The reaction enables the facile preparation of enantioenriched spiro[pyrrolidine-3,3'-oxindole] compounds, which provides a novel strategy for the synthesis of monoterpenoid indole alkaloids. As a demonstration, the asymmetric synthesis of strychnos alkaloids [(-)-tubifoline, (-)-tubifolidine, (-)-dehydrotubifoline] was achieved in 10-11 steps.
The functions of sucrose transporters (SUTs) differ among family members. The physiological function of SUT1 has been studied intensively, while that of SUT4 in various plant species including tomato (Solanum lycopersicum) is less well understood. In this study, we characterized the function of tomato SlSUT4 in the regulation of flowering using a combination of molecular and physiological analyses. SlSUT4 displayed transport activity for sucrose when expressed in yeast (Saccharomyces cerevisiae), and it localized at both the plasma membrane and tonoplast. SlSUT4 interacted with SlSUT1, causing partial internalization of the latter, the main phloem loader of sucrose in tomato. Silencing of SlSUT4 promoted SlSUT1 localization to the plasma membrane, contributing to increased sucrose export and thus increased sucrose level in the shoot apex, which promoted flowering. Both silencing of SlSUT4 and spraying with sucrose suppressed gibberellin biosynthesis through repression of ent-kaurene oxidase and gibberellin 20-oxidase-1 (two genes encoding key enzymes in gibberellin biosynthesis) expression by SlMYB76, which directly bound to their promoters. Silencing of SlMYB76 promoted gibberellin biosynthesis. Our results suggest that SlSUT4 is a functional sucrose transporter in tomato; down-regulation of SlSUT4 expression enhances sucrose transport to the shoot apex, which promotes flowering by inhibiting gibberellin biosynthesis.
Ah ighly enantioselective tandem Michael addition of tryptamine-derived oxindoles to alkynonesw as developed by taking advantage of achiral N,N'-dioxide Sc(OTf) 3 catalyst. The reaction enables the facile preparation of enantioenriched spiro[pyrrolidine-3,3'-oxindole] compounds,w hich provides an ovel strategy for the synthesis of monoterpenoid indole alkaloids.A sademonstration, the asymmetric synthesis of strychnos alkaloids [(À)-tubifoline,( À)-tubifolidine,( À)dehydrotubifoline] was achieved in 10-11 steps.Scheme 2. Substrate scope with respect to alkynones. [a] The reaction was performed with CH 2 Cl 2 as solvent. Cy = cyclohexanyl; Ph = phenyl.Scheme 3. Asymmetric synthesis of strychnos alkaloids.
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