Inherent atomic mobility changes in carbocation intermediates during the sesterterpene cyclization cascade
We previously showed that the regio- and stereoselectivity in terpene-forming reactions are determined by the conformations of the carbocation intermediates, which reflect the initial conformation of the substrate, geranylfarnesyl diphosphate (GFPP). However, it remains unclear how the initial confo...
| Main Authors: | , , , , |
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2019-08-01
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| Series: | Beilstein Journal of Organic Chemistry |
| Subjects: | |
| Online Access: | https://doi.org/10.3762/bjoc.15.184 |
| _version_ | 1818612513241038848 |
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| author | Hajime Sato Takaaki Mitsuhashi Mami Yamazaki Ikuro Abe Masanobu Uchiyama |
| author_facet | Hajime Sato Takaaki Mitsuhashi Mami Yamazaki Ikuro Abe Masanobu Uchiyama |
| author_sort | Hajime Sato |
| collection | DOAJ |
| description | We previously showed that the regio- and stereoselectivity in terpene-forming reactions are determined by the conformations of the carbocation intermediates, which reflect the initial conformation of the substrate, geranylfarnesyl diphosphate (GFPP). However, it remains unclear how the initial conformation of GFPP is controlled, and which part(s) of the GFPP molecule are important for its fixation inside the substrate-binding pocket. Here, we present the first detailed analysis of the inherent atomic mobility in carbocation intermediates during sesterterpene biosynthesis. We identified two methyl groups as the least mobile of all the carbons of the carbocation intermediates in the first half of the cyclization cascade. Our analysis suggests that these two methyl groups are critical for the preorganization of GFPP in the biosynthetic pathways leading to sesterfisherol and quiannulatene. |
| first_indexed | 2024-12-16T15:47:25Z |
| format | Article |
| id | doaj.art-2fc1f70bdfa8408182dbb299145cc87a |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-16T15:47:25Z |
| publishDate | 2019-08-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-2fc1f70bdfa8408182dbb299145cc87a2022-12-21T22:25:46ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972019-08-011511890189710.3762/bjoc.15.1841860-5397-15-184Inherent atomic mobility changes in carbocation intermediates during the sesterterpene cyclization cascadeHajime Sato0Takaaki Mitsuhashi1Mami Yamazaki2Ikuro Abe3Masanobu Uchiyama4Graduate School of Pharmaceutical Sciences, Chiba University, 1-8-1 Inohana, Chuo-ku, Chiba 260-8675, JapanGraduate School of Pharmaceutical Sciences, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanGraduate School of Pharmaceutical Sciences, Chiba University, 1-8-1 Inohana, Chuo-ku, Chiba 260-8675, JapanGraduate School of Pharmaceutical Sciences, University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, JapanClustering of Pioneering Research (CPR) Advanced Elements Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako, Saitama 351-0198, JapanWe previously showed that the regio- and stereoselectivity in terpene-forming reactions are determined by the conformations of the carbocation intermediates, which reflect the initial conformation of the substrate, geranylfarnesyl diphosphate (GFPP). However, it remains unclear how the initial conformation of GFPP is controlled, and which part(s) of the GFPP molecule are important for its fixation inside the substrate-binding pocket. Here, we present the first detailed analysis of the inherent atomic mobility in carbocation intermediates during sesterterpene biosynthesis. We identified two methyl groups as the least mobile of all the carbons of the carbocation intermediates in the first half of the cyclization cascade. Our analysis suggests that these two methyl groups are critical for the preorganization of GFPP in the biosynthetic pathways leading to sesterfisherol and quiannulatene.https://doi.org/10.3762/bjoc.15.184biosynthesiscarbocationDFTsubstrate recognitionterpene cyclase |
| spellingShingle | Hajime Sato Takaaki Mitsuhashi Mami Yamazaki Ikuro Abe Masanobu Uchiyama Inherent atomic mobility changes in carbocation intermediates during the sesterterpene cyclization cascade Beilstein Journal of Organic Chemistry biosynthesis carbocation DFT substrate recognition terpene cyclase |
| title | Inherent atomic mobility changes in carbocation intermediates during the sesterterpene cyclization cascade |
| title_full | Inherent atomic mobility changes in carbocation intermediates during the sesterterpene cyclization cascade |
| title_fullStr | Inherent atomic mobility changes in carbocation intermediates during the sesterterpene cyclization cascade |
| title_full_unstemmed | Inherent atomic mobility changes in carbocation intermediates during the sesterterpene cyclization cascade |
| title_short | Inherent atomic mobility changes in carbocation intermediates during the sesterterpene cyclization cascade |
| title_sort | inherent atomic mobility changes in carbocation intermediates during the sesterterpene cyclization cascade |
| topic | biosynthesis carbocation DFT substrate recognition terpene cyclase |
| url | https://doi.org/10.3762/bjoc.15.184 |
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