Clevenstine E C, Walter P, Harris T M, Broquist H P
Biochemistry. 1979 Aug 21;18(17):3663-7. doi: 10.1021/bi00584a004.
Known or suspected intermediates in the biosynthesis of slaframine and 3,4,5-trihydroxyoctahydro-1-pyrindine, piperidine alkaloids of the phytopathogenic fungus Rhizoctonia leguminicola, were prepared and tested for biological conversions. Ethyl pipecolylacetate, an analogue of the postulated condensation product of pipecolic and malonic acids (two previously identified alkaloid precursors), was insufficiently stable for feeding experiments. The lactam of pipecolylacetate, 1,3-dioxooctahydroindolizine, was degraded by the fungus without direct incorporation into alkaloids. The known slaframine precursor 1-hydroxyoctahydroindolizine was prepared by a novel route which permitted high levels of deuterium enrichment at C-1 and C-3. Mass spectrometric examination of the slaframine biosynthesized from cis- and trans-[1,3,3-2H]-1-hydroxyoctahydroindolizine strengthened arguments that 1-oxooctahydroindolizine is an intermediate in slaframine biogenesis.
制备了植物致病真菌立枯丝核菌的哌啶生物碱——slaframine和3,4,5-三羟基八氢-1-吡啶酮生物合成过程中已知或疑似的中间体，并对其进行生物转化测试。哌啶乙酸乙酯是哌啶酸和丙二酸（两种先前已鉴定的生物碱前体）假定缩合产物的类似物，但其稳定性不足以用于饲养实验。哌啶乙酸乙酯的内酰胺1,3-二氧代八氢吲哚嗪被该真菌降解，未直接掺入生物碱中。已知的slaframine前体1-羟基八氢吲哚嗪通过一种新途径制备，该途径允许在C-1和C-3处进行高水平的氘富集。对由顺式和反式-[1,3,3-2H]-1-羟基八氢吲哚嗪生物合成的slaframine进行质谱分析，进一步证明1-氧代八氢吲哚嗪是slaframine生物合成的中间体。
