4.2.3.63 (2E,6E)-farnesyl diphosphate - Streptomyces sp. (+)-cubenene + diphosphate reaction proceeds via 1,3-hydride shift. (3R)-nerolidyl diphosphate is an intermediate in the cyclization. Cyclization of [ 13,13,13-2H3]farnesy1 diphosphate with crude epicubenol synthase gives [ 13,13,13-2H3]epicubenol ? 413130 4.2.3.63 (2E,6E)-farnesyl diphosphate specific substrate Streptomyces sp. (+)-cubenene + diphosphate - ? 413130 4.2.3.63 (2E,6E)-farnesyl diphosphate specific substrate Streptomyces sp. (+)-cubenene + diphosphate reaction proceeds via 1,2- and 1,3-hydride shifts. (3R)-nerolidyl diphosphate is an intermediate in the cyclization. The initial isomerization of farnesyl diphosphate to (3R)-nerolidyl diphosphate takes place with suprafacial stereochemistry. Ionization of (3R)-nerolidyl diphosphate and attack by the 10-11 double bond on the re face of the cisoid allylic cation-diphosphate anion pair generates the cis-germacradienyl cation. A second electrophilic cyclization gives the cadinanyl cation, which upon a 1.2-hydride shift and syn capture of water generates epicubenol ? 413130 4.2.3.63 (2E,6E)-farnesyl diphosphate specific substrae Heteroscyphus planus (+)-cubenene + diphosphate (+)-cubenene synthase and (+)-epicubenol synthase are dual functions of the same enzyme ? 413130 4.2.3.63 (2E,6E)-farnesyl diphosphate specific substrae Heteroscyphus planus (+)-cubenene + diphosphate reaction proceeds via 1,2- and 1,3-hydride shifts ? 413130 4.2.3.63 (2E,6E)-farnesyl diphosphate - Streptomyces sp. LL-B7 (+)-cubenene + diphosphate reaction proceeds via 1,3-hydride shift. (3R)-nerolidyl diphosphate is an intermediate in the cyclization. Cyclization of [ 13,13,13-2H3]farnesy1 diphosphate with crude epicubenol synthase gives [ 13,13,13-2H3]epicubenol ? 413130 4.2.3.63 (2E,6E)-farnesyl diphosphate specific substrate Streptomyces sp. LL-B7 (+)-cubenene + diphosphate - ? 413130 4.2.3.63 (2E,6E)-farnesyl diphosphate specific substrate Streptomyces sp. LL-B7 (+)-cubenene + diphosphate reaction proceeds via 1,2- and 1,3-hydride shifts. (3R)-nerolidyl diphosphate is an intermediate in the cyclization. The initial isomerization of farnesyl diphosphate to (3R)-nerolidyl diphosphate takes place with suprafacial stereochemistry. Ionization of (3R)-nerolidyl diphosphate and attack by the 10-11 double bond on the re face of the cisoid allylic cation-diphosphate anion pair generates the cis-germacradienyl cation. A second electrophilic cyclization gives the cadinanyl cation, which upon a 1.2-hydride shift and syn capture of water generates epicubenol ? 413130 4.2.3.63 (2E,6E)-farnesyl diphosphate + H2O specific substrate Streptomyces sp. (+)-epicubenol + diphosphate reaction proceeds via 1,2- and 1,3-hydride shifts. (3R)-nerolidyl diphosphate is an intermediate in the cyclization. The initial isomerization of farnesyl diphosphate to (3R)-nerolidyl diphosphate takes place with suprafacial stereochemistry. Ionization of (3R)-nerolidyl diphosphate and attack by the 10-11 double bond on the re face of the cisoid allylic cation-diphosphate anion pair generates the cis-germacradienyl cation. A second electrophilic cyclization gives the cadinanyl cation, which upon a 1.2-hydride shift and syn capture of water generates epicubenol ? 413131 4.2.3.63 (2E,6E)-farnesyl diphosphate + H2O specific substrate Streptomyces sp. LL-B7 (+)-epicubenol + diphosphate reaction proceeds via 1,2- and 1,3-hydride shifts. (3R)-nerolidyl diphosphate is an intermediate in the cyclization. The initial isomerization of farnesyl diphosphate to (3R)-nerolidyl diphosphate takes place with suprafacial stereochemistry. Ionization of (3R)-nerolidyl diphosphate and attack by the 10-11 double bond on the re face of the cisoid allylic cation-diphosphate anion pair generates the cis-germacradienyl cation. A second electrophilic cyclization gives the cadinanyl cation, which upon a 1.2-hydride shift and syn capture of water generates epicubenol ? 413131