Details
| Original language | English |
|---|---|
| Pages (from-to) | 3812-3813 |
| Number of pages | 2 |
| Journal | Journal of the American Chemical Society |
| Volume | 131 |
| Issue number | 11 |
| Publication status | Published - 2 Mar 2009 |
Abstract
The timing of introduction of the unusually placed Δ11,13 diene system in ansamitocin (AP) biosynthesis was probed by synthesizing optically active potential tri- and tetraketide intermediates as their SNAC thioesters. An AP-nonproducing mutant Actinosynnema pretiosum was complemented by the R enantiomer of the triketide and by the tetraketide with rearranged double bonds, but not by the tetraketide carrying the double bonds in conjugation to the thioester function. The results show that the double bonds are installed in their final positions during processing of the nascent polyketide on module 3 of the asm PKS and that KS4 of the PKS acts as a gatekeeper which accepts only a tetraketide with shifted double bonds as substrate for further processing.
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- General Chemistry
- Biochemistry, Genetics and Molecular Biology(all)
- Biochemistry
- Chemical Engineering(all)
- Colloid and Surface Chemistry
Cite this
- Standard
- Harvard
- Apa
- Vancouver
- BibTeX
- RIS
In: Journal of the American Chemical Society, Vol. 131, No. 11, 02.03.2009, p. 3812-3813.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Timing of the Δ10,12-Δ11,13double bond migration during ansamitocin biosynthesis in actinosvnnema pretiosum
AU - Taft, Florian
AU - Brunjes, Marco
AU - Knobloch, Tobias
AU - Floss, Heinz G.
AU - Kirschning, Andreas
PY - 2009/3/2
Y1 - 2009/3/2
N2 - The timing of introduction of the unusually placed Δ11,13 diene system in ansamitocin (AP) biosynthesis was probed by synthesizing optically active potential tri- and tetraketide intermediates as their SNAC thioesters. An AP-nonproducing mutant Actinosynnema pretiosum was complemented by the R enantiomer of the triketide and by the tetraketide with rearranged double bonds, but not by the tetraketide carrying the double bonds in conjugation to the thioester function. The results show that the double bonds are installed in their final positions during processing of the nascent polyketide on module 3 of the asm PKS and that KS4 of the PKS acts as a gatekeeper which accepts only a tetraketide with shifted double bonds as substrate for further processing.
AB - The timing of introduction of the unusually placed Δ11,13 diene system in ansamitocin (AP) biosynthesis was probed by synthesizing optically active potential tri- and tetraketide intermediates as their SNAC thioesters. An AP-nonproducing mutant Actinosynnema pretiosum was complemented by the R enantiomer of the triketide and by the tetraketide with rearranged double bonds, but not by the tetraketide carrying the double bonds in conjugation to the thioester function. The results show that the double bonds are installed in their final positions during processing of the nascent polyketide on module 3 of the asm PKS and that KS4 of the PKS acts as a gatekeeper which accepts only a tetraketide with shifted double bonds as substrate for further processing.
UR - http://www.scopus.com/inward/record.url?scp=67849110452&partnerID=8YFLogxK
U2 - 10.1021/ja8088923
DO - 10.1021/ja8088923
M3 - Article
C2 - 19292483
AN - SCOPUS:67849110452
VL - 131
SP - 3812
EP - 3813
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 11
ER -