一种高效的氧化去芳构化-自由基环化方法，用于合成对称取代的双环黄烷酮天然产物。
An efficient oxidative dearomatization-radical cyclization approach to symmetrically substituted bicyclic guttiferone natural products.
机构信息
Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY, USA.
出版信息
Chem Commun (Camb). 2011 Jan 7;47(1):209-11. doi: 10.1039/c0cc01419b. Epub 2010 Jul 7.
Abstract
Detailed in this communication is an efficient synthetic approach towards the guttiferone family of natural products. Oxidatively unraveling a para-quinone monoketal followed by consecutive 5-exo radical cyclizations provides the bicyclic core. An additional strength of this approach is a late stage asymmetric desymmetrization of an advanced symmetric intermediate.
摘要
本通讯详细介绍了一种高效的合成方法，可用于合成天然产物 gutiferone 家族。通过氧化解开对位醌单缩酮，然后连续进行 5-endo 自由基环化反应，得到双环核心。这种方法的另一个优点是在后期通过不对称去对称化一个高级对称中间体。
相似文献
1
An efficient oxidative dearomatization-radical cyclization approach to symmetrically substituted bicyclic guttiferone natural products.一种高效的氧化去芳构化-自由基环化方法，用于合成对称取代的双环黄烷酮天然产物。
Chem Commun (Camb). 2011 Jan 7;47(1):209-11. doi: 10.1039/c0cc01419b. Epub 2010 Jul 7.
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
Enantioselective total synthesis of hyperforin.手性全合成贯叶金丝桃素。
J Am Chem Soc. 2013 Jan 16;135(2):644-7. doi: 10.1021/ja312150d. Epub 2012 Dec 31.
4
Toward the synthesis of phomoidride D.朝向 phomoidride D 的合成。
J Org Chem. 2013 Jan 18;78(2):477-89. doi: 10.1021/jo302353g. Epub 2013 Jan 10.
5
Synthesis of polyprenylated acylphloroglucinols using bridgehead lithiation: the total synthesis of racemic clusianone and a formal synthesis of racemic garsubellin A.利用桥头锂化反应合成多异戊烯基酰基间苯三酚：外消旋克鲁西酮的全合成及外消旋加苏贝林 A 的形式合成。
J Org Chem. 2007 Jun 22;72(13):4803-15. doi: 10.1021/jo070388h. Epub 2007 May 26.
6
A short biomimetic approach to the fully functionalized bicyclic framework of type A acylphloroglucinols.一种构建A 型酰基间苯三酚全功能化双环骨架的短仿生方法。
Org Lett. 2009 Oct 1;11(19):4430-3. doi: 10.1021/ol901781n.
7
Construction of highly functionalized medium-sized rings: synthesis of hyperforin and perforatumone model systems.高官能化中环的构建：贯叶连翘素和穿叶金丝桃素模型体系的合成
Angew Chem Int Ed Engl. 2005 Jun 20;44(25):3895-9. doi: 10.1002/anie.200500776.
8
Total syntheses of hyperforin and papuaforins A-C, and formal synthesis of nemorosone through a gold(I)-catalyzed carbocyclization.通过金（I）催化的碳环化反应，完成了金丝桃素、 Papuaforin A-C 的全合成以及去甲络石灵的形式合成。
Angew Chem Int Ed Engl. 2014 Jun 23;53(26):6701-4. doi: 10.1002/anie.201403939. Epub 2014 May 18.
9
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.
10
Catalytic asymmetric total synthesis of ent-hyperforin.对映-金丝桃素的催化不对称全合成
Angew Chem Int Ed Engl. 2010 Feb 1;49(6):1103-6. doi: 10.1002/anie.200906678.
引用本文的文献
1
Anticancer Properties and Mechanism of Action of Oblongifolin C, Guttiferone K and Related Polyprenylated Acylphloroglucinols.扁枝杉素C、藤黄双黄酮K及相关多异戊烯基取代酰基间苯三酚的抗癌特性及作用机制
Nat Prod Bioprospect. 2021 Dec;11(6):629-641. doi: 10.1007/s13659-021-00320-1. Epub 2021 Sep 29.
2
Tris(pentafluorophenyl)borane-Catalyzed Reactions Using Silanes.三（五氟苯基）硼烷催化的硅烷反应。
Molecules. 2019 Jan 25;24(3):432. doi: 10.3390/molecules24030432.
3
Formation of Fused Aromatic Architectures via an Oxidative Dearomatization - Radical Cyclization Rearomatization Approach.通过氧化脱芳构化-自由基环化再芳构化方法形成稠合芳族结构。
Tetrahedron Lett. 2015 Jun 3;56(23):3550-3552. doi: 10.1016/j.tetlet.2015.01.110.
4
Enantioselective desymmetrization of prochiral cyclohexanones by organocatalytic intramolecular Michael additions to α,β-unsaturated esters.通过有机催化分子内迈克尔加成至α,β-不饱和酯实现前手性环己酮的对映选择性去对称化反应。
Angew Chem Int Ed Engl. 2015 Apr 13;54(16):4899-903. doi: 10.1002/anie.201411924. Epub 2015 Feb 27.
5
Syntheses and structural confirmations of members of a heterocycle-containing family of labdane diterpenoids.含杂环的半日花烷二萜类化合物家族成员的合成与结构确证
Angew Chem Int Ed Engl. 2013 Jan 28;52(5):1543-7. doi: 10.1002/anie.201208412. Epub 2012 Dec 17.
6
Synthetic Efforts Toward [3.3.1] Bridged Bicyclic Phloroglucinol Natural Products.针对[3.3.1]桥连双环间苯三酚天然产物的合成研究。
Tetrahedron. 2011 Oct 7;67(40):7631-7666. doi: 10.1016/j.tet.2011.06.079.
7
Total synthesis of (±)-7-epi-nemorosone.（±）-7-表愈创木烯的全合成。
Org Lett. 2012 Apr 6;14(7):1796-9. doi: 10.1021/ol300386t. Epub 2012 Mar 26.
8
Recent applications of the (TMS)3SiH radical-based reagent.近期（TMS）3SiH 自由基试剂的应用。
Molecules. 2012 Jan 6;17(1):527-55. doi: 10.3390/molecules17010527.
本文引用的文献
1
Catalytic asymmetric total synthesis of ent-hyperforin.对映-金丝桃素的催化不对称全合成
Angew Chem Int Ed Engl. 2010 Feb 1;49(6):1103-6. doi: 10.1002/anie.200906678.
2
Cytotoxic acylphloroglucinol derivatives from the twigs of Garcinia cowa.来自余甘子树枝的细胞毒性酰基间苯三酚衍生物。
J Nat Prod. 2010 Feb 26;73(2):104-8. doi: 10.1021/np9004147.
3
Polyisoprenylated benzophenones from Clusiaceae: potential drugs and lead compounds.姜科多异戊烯基二苯甲酮类化合物：潜在的药物和先导化合物。
Curr Top Med Chem. 2009;9(16):1560-80. doi: 10.2174/156802609789909830.
4
Effects of garcinol and guttiferone K isolated from Garcinia cambogia on oxidative/nitrative modifications in blood platelets and plasma.藤黄果中分离得到的藤黄酚和新藤黄酸对血小板和血浆氧化/硝化修饰的影响。
Platelets. 2009 Nov;20(7):487-92. doi: 10.3109/09537100903165182.
5
Leishmanicidal activity of benzophenones and extracts from Garcinia brasiliensis Mart. fruits.苯甲酮类化合物和藤黄属植物果实提取物的杀利什曼原虫活性。
Phytomedicine. 2010 Apr;17(5):339-45. doi: 10.1016/j.phymed.2009.07.020. Epub 2009 Sep 16.
6
Antimicrobial activity of benzophenones and extracts from the fruits of Garcinia brasiliensis.巴西藤黄果实中苯甲酮及其提取物的抗菌活性
J Med Food. 2009 Apr;12(2):403-7. doi: 10.1089/jmf.2007.0622.
7
Sirtuin inhibitors.沉默调节蛋白抑制剂
Expert Opin Ther Pat. 2009 Mar;19(3):283-94. doi: 10.1517/13543770902755111.
8
Hyperforin and aristoforin inhibit lymphatic endothelial cell proliferation in vitro and suppress tumor-induced lymphangiogenesis in vivo.金丝桃素和贯叶连翘素在体外抑制淋巴管内皮细胞增殖，并在体内抑制肿瘤诱导的淋巴管生成。
Int J Cancer. 2009 Jul 1;125(1):34-42. doi: 10.1002/ijc.24295.
9
How does SIRT1 affect metabolism, senescence and cancer?沉默调节蛋白1如何影响新陈代谢、衰老和癌症？
Nat Rev Cancer. 2009 Feb;9(2):123-8. doi: 10.1038/nrc2562. Epub 2008 Dec 29.
10
Bioassay-guided isolation of xanthones and polycyclic prenylated acylphloroglucinols from Garcinia oblongifolia.基于生物测定法从长圆叶藤黄中分离出氧杂蒽酮和多环异戊烯基酰基间苯三酚。
J Nat Prod. 2009 Jan;72(1):130-5. doi: 10.1021/np800496c.
Zotero 插件