串联烯炔复分解-金属otropic [1,3]-迁移用于简洁全合成(+)-asperpentyn、(-)-harveynone和(-)-tricholomenyn A。
Tandem enyne metathesis-metallotropic [1,3]-shift for a concise total syntheses of (+)-asperpentyn, (-)-harveynone, and (-)-tricholomenyn A.
作者信息
Li Jingwei, Park Sangho, Miller Reagan L, Lee Daesung
机构信息
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, Illinois 60607, USA.
出版信息
Org Lett. 2009 Feb 5;11(3):571-4. doi: 10.1021/ol802675j.
Abstract
A tandem reaction sequence involving relay metathesis-induced enyne RCM and metallotropic [1,3]-shift is an effective tool to construct cyclic alkenes with embedded 1,5-dien-3-yne moieties from acyclic precursors containing a 1,3-diyne. Total syntheses of (+)-asperpentyn, (-)-harveynone, and (-)-tricholomenyn A have been accomplished by implementing this metathesis-based tandem reaction sequence as the key step.
摘要
一个涉及接力复分解诱导的烯炔关环复分解反应和金属迁移[1,3]迁移的串联反应序列，是从含有1,3 - 二炔的无环前体构建具有嵌入1,5 - 二烯 - 3 - 炔部分的环状烯烃的有效工具。通过将这个基于复分解的串联反应序列作为关键步骤，已完成了(+)-asperpentyn、(-)-harveynone和(-)-tricholomenyn A的全合成。
相似文献
1
Tandem enyne metathesis-metallotropic [1,3]-shift for a concise total syntheses of (+)-asperpentyn, (-)-harveynone, and (-)-tricholomenyn A.
Org Lett. 2009 Feb 5;11(3):571-4. doi: 10.1021/ol802675j.
2
Chemoenzymatic Synthesis of (+)-Asperpentyn and the Enantiomer of the Structure Assigned to Aspergillusol A.
J Nat Prod. 2015 Aug 28;78(8):1963-8. doi: 10.1021/acs.jnatprod.5b00304. Epub 2015 Aug 13.
3
Chemoenzymatic access to versatile epoxyquinol synthons.
Org Lett. 2009 Oct 1;11(19):4290-3. doi: 10.1021/ol9016657.
4
Metathesis and metallotropy: a versatile combination for the synthesis of oligoenynes.
J Am Chem Soc. 2005 Dec 28;127(51):18024-5. doi: 10.1021/ja057153c.
5
Ring synthesis by stereoselective, methylene-free enyne cross metathesis.
J Am Chem Soc. 2004 Jul 7;126(26):8110-1. doi: 10.1021/ja0476922.
6
Total synthesis of (3R,9R,10R)-panaxytriol via tandem metathesis and metallotropic [1,3]-shift as a key step.
Org Lett. 2008 Jan 17;10(2):257-9. doi: 10.1021/ol702651s. Epub 2007 Dec 13.
7
Cross and ring-closing metathesis of 1,3-diynes: metallotropic [1,3]-shift of ruthenium carbenes.
J Am Chem Soc. 2005 Sep 21;127(37):12818-9. doi: 10.1021/ja054875v.
8
Syntheses of natural products having an epoxyquinone structure.
Chem Rev. 2005 Dec;105(12):4515-36. doi: 10.1021/cr040613k.
9
Search for solutions to the reactivity and selectivity problems in enyne metathesis.
Acc Chem Res. 2006 Aug;39(8):509-19. doi: 10.1021/ar050024g.
10
Concise Approach to Cyclohexyne and 1,2-Cyclohexadiene Precursors.
J Org Chem. 2019 Mar 15;84(6):3652-3655. doi: 10.1021/acs.joc.8b03223. Epub 2019 Mar 6.
引用本文的文献
1
Epoxide Stereochemistry Controls Regioselective Ketoreduction in Epoxyquinoid Biosynthesis.
J Am Chem Soc. 2025 Aug 13;147(32):29582-29591. doi: 10.1021/jacs.5c10778. Epub 2025 Jul 29.
2
Structure revision of tricholomenyn B, an antimitotic geranylcyclohexenone rediscovered as a bitter and antibacterial substance, from a basidiomycete Tricholoma japonicum (Shiro-shimeji).
J Antibiot (Tokyo). 2024 Sep;77(9):634-637. doi: 10.1038/s41429-024-00746-y. Epub 2024 May 31.
3
New Antibacterial Chloro-Containing Polyketides from the Alga-Derived Fungus KMM 4696.
J Fungi (Basel). 2022 Apr 27;8(5):454. doi: 10.3390/jof8050454.
4
Biosynthesis of alkyne-containing natural products.
RSC Chem Biol. 2020 Dec 21;2(1):166-180. doi: 10.1039/d0cb00190b. eCollection 2021 Feb 1.
5
Asymmetric synthesis of chiral cycloalkenone derivatives palladium catalysis.
Chem Sci. 2014 Apr 1;5(4):1354-1360. doi: 10.1039/C3SC53250J.
6
Efficient, scalable asymmetric synthesis of an epoxy quinol via Noyori desymmetrization of a meso diketone.
Tetrahedron Asymmetry. 2011 Apr 10;22(7):713-716. doi: 10.1016/j.tetasy.2011.04.022.
7
Structure and reactivity of alkyne-chelated ruthenium alkylidene complexes.
J Am Chem Soc. 2009 Oct 28;131(42):15114-5. doi: 10.1021/ja907155r.
8
Endo-selective enyne ring-closing metathesis promoted by stereogenic-at-Mo monoalkoxide and monoaryloxide complexes. Efficient synthesis of cyclic dienes not accessible through reactions with Ru carbenes.
J Am Chem Soc. 2009 Aug 5;131(30):10652-61. doi: 10.1021/ja904098h.
本文引用的文献
1
Phytotoxins from Tea Gray Blight Fungi, Pestalotiopsis longiseta and Pestalotiopsis theae.
Biosci Biotechnol Biochem. 1992 Jan;56(5):810-1. doi: 10.1271/bbb.56.810.
2
Total synthesis of (3R,9R,10R)-panaxytriol via tandem metathesis and metallotropic [1,3]-shift as a key step.
Org Lett. 2008 Jan 17;10(2):257-9. doi: 10.1021/ol702651s. Epub 2007 Dec 13.
3
Advances in the metallotropic [1,3]-shift of alkynyl carbenoids.
Org Biomol Chem. 2007 Nov 7;5(21):3418-27. doi: 10.1039/b710379d. Epub 2007 Sep 6.
4
Total synthesis and structure assignment of (+)-hexacyclinol.
Angew Chem Int Ed Engl. 2006 Sep 4;45(35):5790-2. doi: 10.1002/anie.200602854.
5
Cross and ring-closing metathesis of 1,3-diynes: metallotropic [1,3]-shift of ruthenium carbenes.
J Am Chem Soc. 2005 Sep 21;127(37):12818-9. doi: 10.1021/ja054875v.
6
Tandem Diels-Alder/ene reactions.
Org Lett. 2004 Sep 2;6(18):3115-7. doi: 10.1021/ol048847d.
7
Relay ring-closing metathesis (RRCM): a strategy for directing metal movement throughout olefin metathesis sequences.
J Am Chem Soc. 2004 Aug 25;126(33):10210-1. doi: 10.1021/ja046385t.
8
Naturally occurring cyclohexane epoxides: sources, biological activities, and synthesis.
Chem Rev. 2004 Jun;104(6):2857-99. doi: 10.1021/cr980013j.
9
Efficient and Z-selective cross-metathesis of conjugated enynes.
Org Lett. 2004 Jun 10;6(12):2035-8. doi: 10.1021/ol049378i.
10
Enyne metathesis (enyne bond reorganization).
Chem Rev. 2004 Mar;104(3):1317-82. doi: 10.1021/cr020009e.
Zotero 插件