Oxidoreductases;
Acting on paired donors, with incorporation or reduction of molecular oxygen;
With reduced flavin or flavoprotein as one donor, and incorporation of one atom of oxygen into the other donor
BRITE hierarchy

(+)-exo-beta-bergamotene,[reduced NADPH---hemoprotein reductase] oxidoreductase (5-dehydro-6-demethoxyfumagillol-producing)

(+)-exo-beta-bergamotene + 2 [reduced NADPH---hemoprotein reductase] + 3 O2 = 5-dehydro-6-demethoxyfumagillol + 2 [oxidized NADPH---hemoprotein reductase] + 3 H2O (overall reaction) [RN:R13117];
(1a) (+)-exo-beta-bergamotene + [reduced NADPH---hemoprotein reductase] + O2 = (5R)-hydroxy-(+)-exo-beta-bergamotene + [oxidized NADPH---hemoprotein reductase] + H2O [RN:R13118];
(1b) (5R)-hydroxy-(+)-exo-beta-bergamotene + O2 = (3S)-3-[2-methyl-3-(3-methylbut-2-en-1-yl)oxiran-2-yl]-4-methylidenecyclohexan-1-one + H2O [RN:R13119];
(1c) (3S)-3-[2-methyl-3-(3-methylbut-2-en-1-yl)oxiran-2-yl]-4-methylidenecyclohexan-1-one + [reduced NADPH---hemoprotein reductase] + O2 = 5-dehydro-6-demethoxyfumagillol + [oxidized NADPH---hemoprotein reductase] + H2O [RN:R13120]

R13117 R13118 R13119 R13120
Reaction

(+)-exo-beta-bergamotene [CPD:C22617];
[reduced NADPH---hemoprotein reductase] [CPD:C03024];
O2 [CPD:C00007];
(5R)-hydroxy-(+)-exo-beta-bergamotene [CPD:C22627];
(3S)-3-[2-methyl-3-(3-methylbut-2-en-1-yl)oxiran-2-yl]-4-methylidenecyclohexan-1-one [CPD:C22628]

The enzyme, characterized from the mold Aspergillus fumigatus, catalyses a complex transformation comprising hydroxylation, bicyclic ring-opening, and two epoxidations, generating the sesquiterpenoid core skeleton of fumagillin.

EC 1.14.14.184 created 2022

1  [PMID:24568283]