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(2E,6E)-farnesyl diphosphate + H2O
(+)-corvol ether B + diphosphate
additional information
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(2E,6E)-farnesyl diphosphate + H2O
(+)-corvol ether B + diphosphate
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(2E,6E)-farnesyl diphosphate + H2O
(+)-corvol ether B + diphosphate
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(2E,6E)-farnesyl diphosphate + H2O
(+)-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, corvol ether is formed through reprotonation of the neutral intermediate
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(2E,6E)-farnesyl diphosphate + H2O
(+)-corvol ether B + diphosphate
(+)-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
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(2E,6E)-farnesyl diphosphate + H2O
(+)-corvol ether B + diphosphate
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
(+)-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
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(2E,6E)-farnesyl diphosphate + H2O
(+)-corvol ether B + diphosphate
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(2E,6E)-farnesyl diphosphate + H2O
(+)-corvol ether B + diphosphate
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-
?
(2E,6E)-farnesyl diphosphate + H2O
(+)-corvol ether B + diphosphate
(+)-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
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?
(2E,6E)-farnesyl diphosphate + H2O
(+)-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, corvol ether is formed through reprotonation of the neutral intermediate
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?
(2E,6E)-farnesyl diphosphate + H2O
(+)-corvol ether B + diphosphate
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
(+)-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
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additional information
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incubation of the purified enzyme with geranyl diposphate yields small amounts of several acyclic and cyclic monoterpenes, with linalool as the main product
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additional information
?
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incubation of the purified enzyme with geranyl diposphate yields small amounts of several acyclic and cyclic monoterpenes, with linalool as the main product
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?
additional information
?
-
incubation of the purified enzyme with geranyl diposphate yields small amounts of several acyclic and cyclic monoterpenes, with linalool as the main product
-
-
?
additional information
?
-
incubation of the purified enzyme with geranyl diposphate yields small amounts of several acyclic and cyclic monoterpenes, with linalool as the main product
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-
?
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Rabe, P.; Pahirulzaman, K.A.; Dickschat, J.S.
Structures and biosynthesis of corvol ethers-sesquiterpenes from the actinomycete Kitasatospora setae
Angew. Chem. Int. Ed. Engl.
54
6041-6045
2015
Kitasatospora setae (E4N7E5), Kitasatospora setae DSM 43861 (E4N7E5)
brenda
Rinkel, J.; Rabe, P.; Garbeva, P.; Dickschat, J.S.
Lessons from 1,3-hydride shifts in sesquiterpene cyclizations
Angew. Chem. Int. Ed. Engl.
55
13593-13596
2016
Kitasatospora setae (E4N7E5), Kitasatospora setae DSM 43861 (E4N7E5)
brenda
Rabe, P.; Janusko, A.; Goldfuss, B.; Dickschat, J.S.
Experimental and theoretical studies on corvol ether biosynthesis
Chembiochem
17
146-149
2016
Kitasatospora setae (E4N7E5), Kitasatospora setae DSM 43861 (E4N7E5)
brenda
Rabe, P.; Dickschat, J.S.
The EIMS fragmentation mechanisms of the sesquiterpenes corvol ethers A and B, epi-cubebol and isodauc-8-en-11-ol
Beilstein J. Org. Chem.
12
1380-1394
2016
Kitasatospora setae, Kitasatospora setae DSM 43861
brenda