EC Number   |
Substrates |
Organism |
Products |
Reversibility |
|---|
  4.2.3.61 | (2E,6E)-farnesyl diphosphate |
- |
Nicotiana tabacum |
(+)-5-epiaristolochene + diphosphate |
- |
? |
| 4.2.3.61 | (2E,6E)-farnesyl diphosphate |
- |
Nicotiana tabacum |
(+)-5-epiaristolochene + diphosphate |
(+)-5-epiaristolochene constitutes about 85% of hyxdrocarbon products |
? |
| 4.2.3.61 | (2E,6E)-farnesyl diphosphate |
- |
Nicotiana tabacum |
(+)-5-epiaristolochene + diphosphate |
about 79% of hydrocarbon product, plus about 6% of (-)-4-epi-eremophilene, 3.6% of (+)-germacrene A and 22 hydrocarbons contributing about 12% of TEAS sesquiterpene products. The pathway to the by-products starts with a 1,6 cyclization of the (Z,E)-farnesyl cation, followed by a 1,2 hydride shift leading to a syn-6,10 ring closure which generates an acoradilyl cation. Elimination of a proton from either C12 or C13 of the isopropylidene tail of the acoradilyl cation readily explains the formation of ?-acoradiene. Alternatively, a 2,11 ring closure followed by elimination of a proton at C2 is the likely pathway to (-)-alpha-cedrene. A 3,11 ring closure of the acoradilyl cation is the most common event, based on the relative abundance of isomerization products observed, and is followed by Wagner-Meerwein rearrangement and proton elimination from C15 to produce isoprezizaene, the dominant (Z,E)-farnesyl cation-derived product |
? |
| 4.2.3.61 | (2E,6E)-farnesyl diphosphate |
- |
Nicotiana attenuata |
(+)-5-epiaristolochene + diphosphate |
single major sesquiterpene product |
? |
| 4.2.3.61 | (2E,6E)-farnesyl diphosphate |
reaction proceeds via geracrene A as an intermediate. Proton donation by residue Y520 is responsible for the activation of germacrene A to a eudesmane cation |
Nicotiana tabacum |
(+)-5-epiaristolochene + diphosphate |
- |
? |
| 4.2.3.61 | (2E,6E)-farnesyl diphosphate |
- |
Nicotiana tabacum |
5-epi-aristolochene + diphosphate |
- |
? |
| 4.2.3.61 | (2E,6Z)-6-fluorofarnesyl diphosphate |
the fluoro substitution at the C6 position of farnesyl diphosphate has negligible effects on enzyme binding, substrate orientation, diphosphate ionization, and the initial 1,10 ring closure catalyzed by TEAS |
Nicotiana tabacum |
(-)-1-fluorogermacrene A |
sole product, 58% yield |
? |
