TY - JOUR
T1 - Biosynthetic precursors of fungal pyrrolizidines, the loline alkaloids
AU - Blankenship, Jimmy D.
AU - Houseknecht, Justin B.
AU - Pal, Sitaram
AU - Bush, Lowell P.
AU - Grossman, Robert B.
AU - Schardl, Christopher L.
PY - 2005/6
Y1 - 2005/6
N2 - 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 endophyte, 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- 2H2]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 γ-substitution reaction.
AB - 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 endophyte, 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- 2H2]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 γ-substitution reaction.
KW - Alkaloids
KW - Biosynthesis
KW - NMR spectroscopy
KW - Natural products
KW - Nitrogen heterocycles
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U2 - 10.1002/cbic.200400327
DO - 10.1002/cbic.200400327
M3 - Article
C2 - 15861432
AN - SCOPUS:17444363904
SN - 1439-4227
VL - 6
SP - 1016
EP - 1022
JO - ChemBioChem
JF - ChemBioChem
IS - 6
ER -