EC Number   |
Substrates |
Organism |
Products |
Reversibility |
|---|
  4.2.3.163 | (2E,6E)-farnesyl diphosphate + H2O |
- |
Kitasatospora setae |
(+)-corvol ether B + diphosphate |
- |
? |
| 4.2.3.163 | (2E,6E)-farnesyl diphosphate + H2O |
(+)-corvol ether B i.e. (1S*,3R*,5aR*,6S*,8aR*)-3,6-dimethyl-1-(propan-2-yl)hexahydro-1H,3H-3,8a-methanocyclopenta[c]oxepine, corvol ether is formed through reprotonation of the neutral intermediate |
Kitasatospora setae |
(+)-corvol ether B + diphosphate |
- |
? |
| 4.2.3.163 | (2E,6E)-farnesyl diphosphate + H2O |
(+)-corvol ether B i.e. (3R,5aR,6S,8aR)-3,6-dimethyl-1-(propan-2-yl)hexahydro-1H,3H-3,8a-methanocyclopenta[c]oxepine. No activity with geranylgeranyl diphosphate. The enzyme forms (+)-corvol ether B and (+)-corvol ether A in the ratio of 3:1 |
Kitasatospora setae |
(+)-corvol ether B + diphosphate |
- |
? |
| 4.2.3.163 | (2E,6E)-farnesyl diphosphate + H2O |
no activity with geranylgeranyl diphosphate. The enzyme forms (+)-corvol ether B and (+)-corvol ether A in the ratio of 3:1. Quantum chemical calculations reveal that a sequence of two 1,2-hydride migrations in the cyclisation cascade from (2E,6E)-farnesyl diphosphate to the corvol ethers A and B are energetically more favourable than an alternative pathway through one 1,3-hydride shift. Because these calculations do not give any insights into what extent the relevant intermediate cations in the two hypothetical cyclisation reactions might be stabilised by the terpene cyclase, isotopic labelling experiments are performed. These pointed to the same enzyme mechanism, thus giving evidence for a cyclisation mechanism through two 1,2-hydride shifts |
Kitasatospora setae |
(+)-corvol ether B + diphosphate |
(+)-corvol ether B i.e. (1S*,3R*,5aR*,6S*,8aR*)-3,6-dimethyl-1-(propan-2-yl)hexahydro-1H,3H-3,8a-methanocyclopenta[c]oxepine |
? |
| 4.2.3.163 | (2E,6E)-farnesyl diphosphate + H2O |
- |
Kitasatospora setae DSM 43861 |
(+)-corvol ether B + diphosphate |
- |
? |
| 4.2.3.163 | (2E,6E)-farnesyl diphosphate + H2O |
(+)-corvol ether B i.e. (3R,5aR,6S,8aR)-3,6-dimethyl-1-(propan-2-yl)hexahydro-1H,3H-3,8a-methanocyclopenta[c]oxepine. No activity with geranylgeranyl diphosphate. The enzyme forms (+)-corvol ether B and (+)-corvol ether A in the ratio of 3:1 |
Kitasatospora setae DSM 43861 |
(+)-corvol ether B + diphosphate |
- |
? |
| 4.2.3.163 | (2E,6E)-farnesyl diphosphate + H2O |
(+)-corvol ether B i.e. (1S*,3R*,5aR*,6S*,8aR*)-3,6-dimethyl-1-(propan-2-yl)hexahydro-1H,3H-3,8a-methanocyclopenta[c]oxepine, corvol ether is formed through reprotonation of the neutral intermediate |
Kitasatospora setae DSM 43861 |
(+)-corvol ether B + diphosphate |
- |
? |
| 4.2.3.163 | (2E,6E)-farnesyl diphosphate + H2O |
no activity with geranylgeranyl diphosphate. The enzyme forms (+)-corvol ether B and (+)-corvol ether A in the ratio of 3:1. Quantum chemical calculations reveal that a sequence of two 1,2-hydride migrations in the cyclisation cascade from (2E,6E)-farnesyl diphosphate to the corvol ethers A and B are energetically more favourable than an alternative pathway through one 1,3-hydride shift. Because these calculations do not give any insights into what extent the relevant intermediate cations in the two hypothetical cyclisation reactions might be stabilised by the terpene cyclase, isotopic labelling experiments are performed. These pointed to the same enzyme mechanism, thus giving evidence for a cyclisation mechanism through two 1,2-hydride shifts |
Kitasatospora setae DSM 43861 |
(+)-corvol ether B + diphosphate |
(+)-corvol ether B i.e. (1S*,3R*,5aR*,6S*,8aR*)-3,6-dimethyl-1-(propan-2-yl)hexahydro-1H,3H-3,8a-methanocyclopenta[c]oxepine |
? |
| 4.2.3.163 | more |
incubation of the purified enzyme with geranyl diposphate yields small amounts of several acyclic and cyclic monoterpenes, with linalool as the main product |
Kitasatospora setae |
? |
- |
? |
| 4.2.3.163 | more |
incubation of the purified enzyme with geranyl diposphate yields small amounts of several acyclic and cyclic monoterpenes, with linalool as the main product |
Kitasatospora setae DSM 43861 |
? |
- |
? |
