手性全合成及streptorubin B 的绝对和相对立体化学的确认。
Enantioselective total synthesis and confirmation of the absolute and relative stereochemistry of streptorubin B.
机构信息
Northwestern University.
出版信息
J Am Chem Soc. 2011 Feb 16;133(6):1799-804. doi: 10.1021/ja109165f. Epub 2010 Dec 17.
Abstract
The enantioselective total synthesis of the pyrrolophane natural product streptorubin B is described. Key steps in the concise route include the application of a one-pot enantioselective aldol cyclization/Wittig reaction and an anionic oxy-Cope rearrangement to forge the crucial 10-membered ring. Comparisons between CD spectra of synthetic and natural samples of streptorubin B coupled with X-ray crystallography allowed for the determination of the absolute stereochemistry of this natural product for the first time. These studies also provided unambiguous proof of the relative configuration between the butyl side chain and the bispyrrole subunit. Additional studies revealed a novel atropstereoselective Paal-Knorr pyrrole condensation and provided fundamental experimental insight into the barrier for atropisomerization of the natural product.
摘要
本文描述了吡咯并菲烷天然产物streptorubin B 的对映选择性全合成。简洁路线中的关键步骤包括应用一锅对映选择性羟醛环化/Wittig 反应和负离子氧-Cope 重排来构建关键的 10 元环。streptorubin B 的合成和天然样品的 CD 光谱比较以及 X 射线晶体学分析首次确定了该天然产物的绝对立体化学。这些研究还提供了丁基侧链和双吡咯亚基之间的相对构型的明确证据。进一步的研究揭示了一种新的对映选择性 Paal-Knorr 吡咯缩合反应，并为天然产物的对映体异构化势垒提供了基本的实验见解。
相似文献
1
Enantioselective total synthesis and confirmation of the absolute and relative stereochemistry of streptorubin B.手性全合成及streptorubin B 的绝对和相对立体化学的确认。
J Am Chem Soc. 2011 Feb 16;133(6):1799-804. doi: 10.1021/ja109165f. Epub 2010 Dec 17.
2
Stereochemical elucidation of streptorubin B.streptorubin B 的立体化学阐明。
J Am Chem Soc. 2011 Feb 16;133(6):1793-8. doi: 10.1021/ja109164t. Epub 2010 Dec 17.
3
Elimination of butylcycloheptylprodigiosin as a known natural product inspired by an evolutionary hypothesis for cyclic prodigiosin biosynthesis.消除丁基环庚基灵菌红素作为一种已知的天然产物，这是基于环灵菌红素生物合成的进化假说。
J Nat Prod. 2013 Oct 25;76(10):1937-45. doi: 10.1021/np400531b. Epub 2013 Sep 20.
4
Enantioselective Total Synthesis of (+)-Steenkrotin A and Determination of Its Absolute Configuration.(+)-Steenkrotin A的对映选择性全合成及其绝对构型的确定。
Chemistry. 2016 Jan 18;22(3):959-70. doi: 10.1002/chem.201503831. Epub 2015 Dec 11.
5
Synthesis and structural reconfirmation of bacillamide B.杆菌酰胺B的合成与结构再确认
Org Biomol Chem. 2015 Apr 14;13(14):4271-7. doi: 10.1039/c5ob00093a. Epub 2015 Mar 11.
6
Perylenequinone natural products: total synthesis of hypocrellin A.二萘嵌苯醌天然产物：血卟啉 A 的全合成。
J Org Chem. 2010 Jan 1;75(1):57-68. doi: 10.1021/jo901386d.
7
Stereochemistry and Mechanism of Undecylprodigiosin Oxidative Carbocyclization to Streptorubin B by the Rieske Oxygenase RedG.瑞氏氧化物酶 RedG 介导的深红紫素 B 氧化碳环化反应的立体化学和机制。
J Am Chem Soc. 2015 Jun 24;137(24):7889-97. doi: 10.1021/jacs.5b03994. Epub 2015 Jun 12.
8
Enantioselective Total Synthesis of (-)-Rubriflordilactone B by a Bioinspired Skeletal Reorganization Approach.通过仿生骨架重组方法对(-)-红紫素内酯B进行对映选择性全合成。
J Am Chem Soc. 2025 Mar 5;147(9):7875-7885. doi: 10.1021/jacs.4c18292. Epub 2025 Feb 17.
9
Total synthesis of the congested propellane alkaloid (-)-acutumine.拥挤丙二烯生物碱（-）-刺桐灵的全合成。
Chem Rec. 2014 Aug;14(4):580-91. doi: 10.1002/tcr.201400005. Epub 2014 May 23.
10
Development of a merged conjugate addition/oxidative coupling sequence. Application to the enantioselective total synthesis of metacycloprodigiosin and prodigiosin R1.一种合并的共轭加成/氧化偶联序列的开发。其在间环原放线菌素和原放线菌素R1的对映选择性全合成中的应用。
J Am Chem Soc. 2009 Oct 14;131(40):14579-83. doi: 10.1021/ja906122g.
引用本文的文献
1
Stereocontrol in Conformationally Stable C(sp)─C(sp) Atropisomers.构象稳定的C(sp)─C(sp)阻转异构体中的立体控制
Angew Chem Int Ed Engl. 2025 Jul 7;64(28):e202506810. doi: 10.1002/anie.202506810. Epub 2025 May 24.
2
Uridine natural products: Challenging targets and inspiration for novel small molecule inhibitors.尿苷天然产物：具有挑战性的靶标和新型小分子抑制剂的灵感来源。
Bioorg Med Chem. 2020 Sep 15;28(18):115661. doi: 10.1016/j.bmc.2020.115661. Epub 2020 Jul 30.
3
Natural products as inspiration for the development of bacterial antibiofilm agents.天然产物可作为开发细菌抗生物膜剂的灵感来源。
Nat Prod Rep. 2020 Nov 1;37(11):1454-1477. doi: 10.1039/d0np00022a. Epub 2020 Jul 1.
4
Ion Mobility Mass Spectrometry as an Efficient Tool for Identification of Streptorubin B in M145.离子淌度质谱分析作为鉴定 M145 中 Streptorubin B 的有效工具。
J Nat Prod. 2020 Jan 24;83(1):159-163. doi: 10.1021/acs.jnatprod.9b00828. Epub 2020 Jan 6.
5
Construction of Polycyclic γ-Lactams and Related Heterocycles via Electron Catalysis.通过电子催化构建多环 γ-内酰胺和相关杂环化合物。
Org Lett. 2016 Dec 16;18(24):6372-6375. doi: 10.1021/acs.orglett.6b03267. Epub 2016 Nov 29.
6
Structure, Chemical Synthesis, and Biosynthesis of Prodiginine Natural Products.灵菌红素天然产物的结构、化学合成及生物合成
Chem Rev. 2016 Jul 27;116(14):7818-53. doi: 10.1021/acs.chemrev.6b00024. Epub 2016 Jun 17.
7
Enantioselective synthesis of metacycloprodigiosin via the "Wasserman pyrrole".通过“瓦瑟曼吡咯”对间环丙基灵菌红素进行对映选择性合成。
Tetrahedron Lett. 2015 Jun 3;56(23):3228-3230. doi: 10.1016/j.tetlet.2014.12.075.
8
Synthesis of Cycloprodigiosin Identifies the Natural Isolate as a Scalemic Mixture.环丙基灵菌红素的合成确定天然分离物为外消旋混合物。
Org Lett. 2015 Jul 17;17(14):3474-7. doi: 10.1021/acs.orglett.5b01527. Epub 2015 Jun 26.
9
Mechanism and Catalytic Diversity of Rieske Non-Heme Iron-Dependent Oxygenases.赖氏非血红素铁依赖性加氧酶的作用机制与催化多样性
ACS Catal. 2013 Oct 4;3(10). doi: 10.1021/cs400087p.
10
Elimination of butylcycloheptylprodigiosin as a known natural product inspired by an evolutionary hypothesis for cyclic prodigiosin biosynthesis.消除丁基环庚基灵菌红素作为一种已知的天然产物，这是基于环灵菌红素生物合成的进化假说。
J Nat Prod. 2013 Oct 25;76(10):1937-45. doi: 10.1021/np400531b. Epub 2013 Sep 20.
本文引用的文献
1
Evaluation of the biosynthetic proposal for the synthesis of marineosins A and B.海洋霉素 A 和 B 生物合成方案的评估。
Org Lett. 2010 Mar 5;12(5):1048-51. doi: 10.1021/ol100034p.
2
Development of a merged conjugate addition/oxidative coupling sequence. Application to the enantioselective total synthesis of metacycloprodigiosin and prodigiosin R1.一种合并的共轭加成/氧化偶联序列的开发。其在间环原放线菌素和原放线菌素R1的对映选择性全合成中的应用。
J Am Chem Soc. 2009 Oct 14;131(40):14579-83. doi: 10.1021/ja906122g.
3
A prodigiosin from the roseophilin producer Streptomyces griseoviridis.来自玫瑰嗜铁菌素产生菌灰绿链霉菌的灵菌红素。
J Nat Prod. 2008 Jul;71(7):1265-7. doi: 10.1021/np7007494. Epub 2008 Jun 14.
4
Elucidation of the Streptomyces coelicolor pathway to 2-undecylpyrrole, a key intermediate in undecylprodiginine and streptorubin B biosynthesis.天蓝色链霉菌合成2-十一烷基吡咯的途径解析，2-十一烷基吡咯是十一烷基灵菌红素和链霉红菌素B生物合成中的关键中间体。
Chem Biol. 2008 Feb;15(2):137-48. doi: 10.1016/j.chembiol.2007.11.015.
5
Anticancer and immunosuppressive properties of bacterial prodiginines.细菌灵菌红素的抗癌和免疫抑制特性。
Future Microbiol. 2007 Dec;2(6):605-18. doi: 10.2217/17460913.2.6.605.
6
Small molecule obatoclax (GX15-070) antagonizes MCL-1 and overcomes MCL-1-mediated resistance to apoptosis.小分子 obatoclax（GX15 - 070）可拮抗MCL - 1并克服MCL - 1介导的细胞凋亡抗性。
Proc Natl Acad Sci U S A. 2007 Dec 4;104(49):19512-7. doi: 10.1073/pnas.0709443104. Epub 2007 Nov 26.
7
Mosher ester analysis for the determination of absolute configuration of stereogenic (chiral) carbinol carbons.用于测定手性甲醇碳绝对构型的莫舍尔酯分析。
Nat Protoc. 2007;2(10):2451-8. doi: 10.1038/nprot.2007.354.
8
A concise synthesis of butylcycloheptylprodigiosin.
Org Lett. 2007 May 10;9(10):1879-81. doi: 10.1021/ol070341i. Epub 2007 Apr 18.
9
The biosynthesis and regulation of bacterial prodiginines.细菌灵杆菌素的生物合成与调控
Nat Rev Microbiol. 2006 Dec;4(12):887-99. doi: 10.1038/nrmicro1531.
10
A convenient and genuine equivalent to HZrCp2Cl generated in situ from ZrCp2Cl2-DIBAL-H.一种由二氯二茂锆（ZrCp₂Cl₂）-二异丁基氢化铝（DIBAL-H）原位生成的便捷且纯正的二氯氢锆茂（HZrCp₂Cl）等效物。
Org Lett. 2006 Aug 17;8(17):3675-8. doi: 10.1021/ol061202o.
Zotero 插件