穿越生物合成碳正离子景观实现安特拉丁和特瑞酮烯类混合萜的全合成。
Traversing Biosynthetic Carbocation Landscapes in the Total Synthesis of Andrastin and Terretonin Meroterpenes.
机构信息
Department of Chemistry, University of California, Berkeley, 826 Latimer Hall, Berkeley, CA, 94720, USA.
Department of Chemistry, Yale University, 275 Prospect Street, New Haven, CT, 06520, USA.
出版信息
Angew Chem Int Ed Engl. 2017 Oct 2;56(41):12498-12502. doi: 10.1002/anie.201705654. Epub 2017 Aug 30.
Abstract
Meroterpenes derived from dimethylorsellinic acid (DMOA) and farnesyl pyrophosphate have attracted much biosynthetic attention, yet only recently have synthetic solutions to any family members appeared. A key point of divergence in DMOA-derived meroterpene biosynthesis is the protoaustinoid A carbocation, which can be diverted to either the berkeleyone, andrastin, or terretonin structural classes by cyclase-controlled rearrangement pathways. Shown herein is that the protoaustinoid bicyclo[3.3.1]nonane nucleus can be reverted to either andrastin or terretonin ring systems under abiotic reaction conditions. The first total syntheses of members of these natural product families are reported as their racemates.
摘要
二甲奥尔烯酸（DMOA）和法呢基焦磷酸衍生的倍半萜烯引起了人们对生物合成的极大关注，但直到最近才出现了针对任何家族成员的合成解决方案。DMOA 衍生的倍半萜烯生物合成中一个关键的分歧点是原阿替丁 A 碳正离子，它可以通过环化酶控制的重排途径转化为伯克利酮、阿替丁或特里顿宁结构类别。本文表明，在非生物反应条件下，原阿替丁双环[3.3.1]壬烷核可以重新转化为阿替丁或特里顿宁环系。这些天然产物家族成员的首次全合成作为外消旋体进行了报道。
相似文献
1
Traversing Biosynthetic Carbocation Landscapes in the Total Synthesis of Andrastin and Terretonin Meroterpenes.穿越生物合成碳正离子景观实现安特拉丁和特瑞酮烯类混合萜的全合成。
Angew Chem Int Ed Engl. 2017 Oct 2;56(41):12498-12502. doi: 10.1002/anie.201705654. Epub 2017 Aug 30.
2
Annulative Methods in the Synthesis of Complex Meroterpene Natural Products.环合方法在复杂倍半萜天然产物合成中的应用。
Acc Chem Res. 2021 Feb 2;54(3):583-594. doi: 10.1021/acs.accounts.0c00781. Epub 2021 Jan 15.
3
Annulative Methods Enable a Total Synthesis of the Complex Meroterpene Berkeleyone A.环合方法可实现复杂倍半萜伯克利酮 A 的全合成。
J Am Chem Soc. 2016 Nov 16;138(45):14868-14871. doi: 10.1021/jacs.6b10397. Epub 2016 Nov 8.
4
Programmable meroterpene synthesis.可编程的混合萜类合成。
Nat Commun. 2020 Jan 24;11(1):508. doi: 10.1038/s41467-020-14354-5.
5
Revision of the Peniroquesine Biosynthetic Pathway by Retro-Biosynthetic Theoretical Analysis: Ring Strain Controls the Unique Carbocation Rearrangement Cascade.通过逆生物合成理论分析对 Peniroquesine 生物合成途径的修正：环张力控制独特的碳正离子重排级联反应。
JACS Au. 2023 May 15;3(6):1596-1603. doi: 10.1021/jacsau.3c00039. eCollection 2023 Jun 26.
6
Total Synthesis of (±)-Berkeleyone A.（±）-Berkeleyone A 的全合成。
J Am Chem Soc. 2017 Feb 8;139(5):1790-1793. doi: 10.1021/jacs.6b12914. Epub 2017 Jan 27.
7
Enantioselective Total Synthesis of Berkeleyone A and Preaustinoids.手性全合成伯克利酮 A 和前澳斯汀类化合物。
Angew Chem Int Ed Engl. 2021 Jun 25;60(27):14869-14874. doi: 10.1002/anie.202104014. Epub 2021 May 24.
8
Biomimetic Dearomatization Strategies in the Total Synthesis of Meroterpenoid Natural Products.仿生去芳构化策略在倍半萜类天然产物全合成中的应用。
Acc Chem Res. 2021 Apr 20;54(8):1843-1855. doi: 10.1021/acs.accounts.1c00019. Epub 2021 Apr 1.
9
Uncovering the unusual D-ring construction in terretonin biosynthesis by collaboration of a multifunctional cytochrome P450 and a unique isomerase.揭示 Terretonin 生物合成中多功能细胞色素 P450 和独特异构酶协作的不寻常 D 环结构。
J Am Chem Soc. 2015 Mar 11;137(9):3393-401. doi: 10.1021/jacs.5b00570. Epub 2015 Feb 25.
10
Meroterpenes from Dichrostachys cinerea inhibit protein farnesyl transferase activity.
J Nat Prod. 2009 Oct;72(10):1804-15. doi: 10.1021/np900095z.
引用本文的文献
1
Evolution of a Strategy for the Unified, Asymmetric Total Syntheses of DMOA-Derived Spiromeroterpenoids.一种用于DMOA衍生的螺旋萜类化合物统一、不对称全合成策略的演变
J Org Chem. 2024 Sep 6;89(17):11891-11908. doi: 10.1021/acs.joc.4c01116. Epub 2024 Aug 12.
2
3
Biogenetic space-guided synthesis of rearranged terpenoids.生物遗传空间导向的萜类重排合成。
Chem Commun (Camb). 2023 Jun 1;59(45):6811-6826. doi: 10.1039/d3cc01009k.
4
Unified, Asymmetric Total Synthesis of the Asnovolins and Related Spiromeroterpenoids: A Fragment Coupling Approach.统一的、非对称全合成阿索诺林及其相关螺旋缩酮类化合物：片段偶联方法。
J Am Chem Soc. 2022 Jul 20;144(28):12970-12978. doi: 10.1021/jacs.2c05366. Epub 2022 Jul 6.
5
Total Synthesis of Natural Terpenoids Enabled by Cobalt Catalysis.钴催化实现天然萜类化合物的全合成。
Front Chem. 2022 Jun 15;10:941184. doi: 10.3389/fchem.2022.941184. eCollection 2022.
6
Intramolecular Tricarbonyl-Ene Reactions and α-Hydroxy-β-Diketone Rearrangements Inspired by the Biosynthesis of Polycyclic Polyprenylated Acylphloroglucinols.受多环聚异戊烯基酰基间苯三酚的生物合成启发的分子内三羰基-烯反应和α-羟基-β-二酮重排。
Angew Chem Int Ed Engl. 2022 Aug 22;61(34):e202203311. doi: 10.1002/anie.202203311. Epub 2022 Jul 14.
7
Chemical investigations into the biosynthesis of the gymnastatin and dankastatin alkaloids.对裸盖菇素和丹卡他汀生物碱生物合成的化学研究。
Chem Sci. 2021 May 31;12(25):8884-8891. doi: 10.1039/d1sc02613e. eCollection 2021 Jul 1.
8
Highly chemoselective synthesis of hindered amides via cobalt-catalyzed intermolecular oxidative hydroamidation.钴催化的分子间氧化氨化反应高化学选择性合成受阻酰胺。
Nat Commun. 2021 May 5;12(1):2552. doi: 10.1038/s41467-021-22373-z.
9
Stereocontrolled Radical Bicyclizations of Oxygenated Precursors Enable Short Syntheses of Oxidized Abietane Diterpenoids.立体控制的含氧前体自由基环化反应可实现氧化松香烷二萜的短合成路线。
J Am Chem Soc. 2021 Feb 24;143(7):2944-2952. doi: 10.1021/jacs.0c13300. Epub 2021 Feb 8.
10
Recent Progress in Steroid Synthesis Triggered by the Emergence of New Catalytic Methods.新催化方法的出现引发的甾体合成研究新进展
European J Org Chem. 2020 Feb 21;2020(7):755-776. Epub 2020 Jan 1.
本文引用的文献
1
Discovery of an Extended Austinoid Biosynthetic Pathway in Aspergillus calidoustus.在嗜热曲霉中发现扩展的奥斯汀类生物合成途径。
ACS Chem Biol. 2017 May 19;12(5):1227-1234. doi: 10.1021/acschembio.7b00003. Epub 2017 Mar 15.
2
Total Synthesis of (±)-Berkeleyone A.（±）-Berkeleyone A 的全合成。
J Am Chem Soc. 2017 Feb 8;139(5):1790-1793. doi: 10.1021/jacs.6b12914. Epub 2017 Jan 27.
3
Fe-Catalyzed C-C Bond Construction from Olefins via Radicals.铁催化的自由基途径构建烯烃碳-碳键。
J Am Chem Soc. 2017 Feb 15;139(6):2484-2503. doi: 10.1021/jacs.6b13155. Epub 2017 Feb 2.
4
Annulative Methods Enable a Total Synthesis of the Complex Meroterpene Berkeleyone A.环合方法可实现复杂倍半萜伯克利酮 A 的全合成。
J Am Chem Soc. 2016 Nov 16;138(45):14868-14871. doi: 10.1021/jacs.6b10397. Epub 2016 Nov 8.
5
Discovery of Key Dioxygenases that Diverged the Paraherquonin and Acetoxydehydroaustin Pathways in Penicillium brasilianum.发现关键双氧酶，使巴西青霉中的副麦角甾酮和乙酰脱氢澳麦角甾醇途径分化。
J Am Chem Soc. 2016 Sep 28;138(38):12671-7. doi: 10.1021/jacs.6b08424. Epub 2016 Sep 16.
6
Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins.锰、铁和钴催化的烯烃自由基氢官能化反应
Chem Rev. 2016 Aug 10;116(15):8912-9000. doi: 10.1021/acs.chemrev.6b00334. Epub 2016 Jul 27.
7
Cytochrome P450 for Citreohybridonol Synthesis: Oxidative Derivatization of the Andrastin Scaffold.细胞色素 P450 用于合成柠檬酸异 hybridonol：安特拉斯汀支架的氧化衍生化。
Org Lett. 2016 Jan 15;18(2):296-9. doi: 10.1021/acs.orglett.5b03465. Epub 2016 Jan 5.
8
Unusual chemistries in fungal meroterpenoid biosynthesis.真菌聚酮萜类生物合成中的异常化学性质。
Curr Opin Chem Biol. 2016 Apr;31:1-7. doi: 10.1016/j.cbpa.2015.11.001. Epub 2015 Nov 21.
9
Biosynthesis of fungal meroterpenoids.真菌生源二萜类化合物的生物合成。
Nat Prod Rep. 2016 Jan;33(1):26-53. doi: 10.1039/c5np00090d.
10
Uncovering the unusual D-ring construction in terretonin biosynthesis by collaboration of a multifunctional cytochrome P450 and a unique isomerase.揭示 Terretonin 生物合成中多功能细胞色素 P450 和独特异构酶协作的不寻常 D 环结构。
J Am Chem Soc. 2015 Mar 11;137(9):3393-401. doi: 10.1021/jacs.5b00570. Epub 2015 Feb 25.
Zotero 插件