Biosynthetic precursors of fungal pyrrolizidines, the loline alkaloids
Biosynthetic precursors of fungal pyrrolizidines, the loline alkaloids
复制标题
DOI：
10.1002/cbic.200400327
复制
发表时间：
2005-06-01
期刊：
影响因子：
3.2
通讯作者：
Schardl, CL
中科院分区：
文献类型：
--
作者：
Blankenship, JD;Houseknecht, JB;Schardl, CL
洛林生物碱是一种饱和的吡咯烷，具有取代的1-氨基和C2和C7之间的氧桥，并且是植物共生真菌（内生菌）的杀虫代谢物。培养的藻类，钩状新伤寒，纳入标记的L-脯氨酸和L-高丝氨酸的1-氨基吡咯里西啶，N-甲酰吗啉。A-环碳C1-C3和N1衍生自L-高丝氨酸; B-环碳C5-C8和环氮衍生自L-脯氨酸。从L-[4，4-H-2（2）]高丝氨酸掺入两个氘原子和用标记的L-甲硫氨酸进行的喂养试验表明，L-高丝氨酸掺入不是通过乙酰半醛或S-腺苷甲硫氨酸实现的，而是可能涉及高度新颖的N-C键形成γ-取代反应。
Loline alkaloids are saturated pyrrolizidines with a substituted 1-amino group and an oxygen bridge between C2 and C7, and are insecticidal metabolites of plant-symbiotic fungi (endophytes). Cultures of the enclophyte, Neotyphodium uncinatum, incorporated labeled L-proline and L-homoserine into the 1-aminopyrrolizidine, N-formylloline. The A-ring carbons C1-C3 and the N1 were derived from L-homoserine; the B-ring carbons C5-C8 and the ring nitrogen were derived from L-proline. Incorporation of both deuterium atoms from L-[4,4-H-2(2)]homoserine and feeding tests with labeled L-methionine indicated that L-homoserine incorporation was not achieved via aspartyl semialdehyde or S-adenosylmethionine, but probably involved a highly novel N-C bond-forming gamma-substitution reaction.