螺环亚胺部分的合成及海洋霉素 A 和 B 的合成方法。
Synthesis of the spiroiminal moiety and approaches to the synthesis of marineosins A and B.
机构信息
Department of Chemistry, Brandeis University , MS 015, Waltham, Massachusetts 02454-9110, United States.
出版信息
J Org Chem. 2013 Dec 6;78(23):12161-75. doi: 10.1021/jo402178r. Epub 2013 Nov 21.
Abstract
A short and efficient synthesis of model spiroiminals that have the same stereochemistry as marineosins A and B, but different conformations, was carried out in six or seven steps from 6-methyltetrahydropyran-2-one. These spiroiminals were also prepared biomimetically by reduction of an enol ether. A more highly substituted spiroiminal with the same stereochemistry and conformation as marineosin A was prepared in 11 steps from parasorbic acid. A macrocyclic pyrrole lactone was prepared stereospecifically in 10 steps. A five-step sequence converted the lactone to a late hemi-iminal intermediate that has resisted the methylation and spiroiminal formation that would lead to marineosin A.
摘要
从 6-甲基四氢吡喃-2-酮出发，经六至七步反应，以中等总收率合成了与海洋霉素 A 和 B 具有相同立体化学而构象不同的模型螺环亚胺。这些螺环亚胺也可以通过烯醇醚的还原来生物模拟合成。用对伞花酸经 11 步反应以中等总收率合成了与海洋霉素 A 具有相同立体化学和构象的取代程度更高的螺环亚胺。用立体专一的 10 步反应合成了一个大环吡咯内酰胺。通过五步反应将内酰胺转化为一个半亚胺中间体，该中间体阻止了进一步的甲基化和螺环亚胺化反应，从而生成海洋霉素 A。
相似文献
1
Synthesis of the spiroiminal moiety and approaches to the synthesis of marineosins A and B.螺环亚胺部分的合成及海洋霉素 A 和 B 的合成方法。
J Org Chem. 2013 Dec 6;78(23):12161-75. doi: 10.1021/jo402178r. Epub 2013 Nov 21.
2
Synthesis of the spiroiminal moiety of marineosins A and B.海洋奥辛 A 和 B 的螺环亚胺部分的合成。
Org Lett. 2010 Apr 2;12(7):1600-3. doi: 10.1021/ol100333d.
3
A concise approach to the spiroiminal fragment of marineosins.海洋奥辛斯螺环片段的简洁方法。
Org Biomol Chem. 2013 May 14;11(18):2936-8. doi: 10.1039/c3ob40208h.
4
Anomalous Chromophore Disruption Enables an Eight-Step Synthesis and Stereochemical Reassignment of (+)-Marineosin A.异常生色团破坏使 (+)-海洋霉素 A 的八步合成和立体化学重排成为可能。
J Am Chem Soc. 2019 Feb 13;141(6):2274-2278. doi: 10.1021/jacs.9b00396. Epub 2019 Jan 31.
5
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.
6
Total synthesis of (-)-sessilifoliamide J.(-)- sessilifoliamide J 的全合成
J Org Chem. 2013 Jan 4;78(1):35-41. doi: 10.1021/jo3014484. Epub 2012 Sep 14.
7
Synthesis of stereoisomers of Artemisia and Chrysanthemum bis(acetylenic) enol ether spiroacetals.合成蒿和菊双（炔基）烯醇缩醚螺缩酮的立体异构体。
J Org Chem. 2012 Dec 7;77(23):10623-30. doi: 10.1021/jo301810d. Epub 2012 Nov 14.
8
Asymmetric Total Syntheses of ent-Ascospiroketals A and B.ent-Ascospiroketals A 和 B 的非对映全合成。
Org Lett. 2016 Apr 15;18(8):1936-9. doi: 10.1021/acs.orglett.6b00796. Epub 2016 Apr 4.
9
A diastereoselective formal synthesis of berkelic acid.手性选择性的贝拉酸的形式合成。
Org Lett. 2011 Jan 7;13(1):118-21. doi: 10.1021/ol102652t. Epub 2010 Dec 7.
10
Cephalostatin analogues--synthesis and biological activity.头霉素类似物——合成与生物活性
Fortschr Chem Org Naturst. 2004;87:1-80. doi: 10.1007/978-3-7091-0581-8_1.
引用本文的文献
1
Functionalized in Triplicate: A Ring-By-Ring Approach to Tailored Prodiginine Derivatives for Site-Specific Conjugation Through Click Chemistry.三重功能化：一种通过点击化学实现位点特异性共轭的定制前药衍生物的逐环方法。
Chemistry. 2025 Aug 1;31(43):e202502066. doi: 10.1002/chem.202502066. Epub 2025 Jul 14.
2
Marine Pyrrole Alkaloids.海洋吡咯生物碱。
Mar Drugs. 2021 Sep 10;19(9):514. doi: 10.3390/md19090514.
3
MarH, a Bifunctional Enzyme Involved in the Condensation and Hydroxylation Steps of the Marineosin Biosynthetic Pathway.MarH，一种参与海洋素生物合成途径缩合和羟化步骤的双功能酶。
Org Lett. 2017 Mar 17;19(6):1298-1301. doi: 10.1021/acs.orglett.7b00093. Epub 2017 Mar 8.
4
Stereospecific synthesis of 23-hydroxyundecylprodiginines and analogues and conversion to antimalarial premarineosins via a Rieske oxygenase catalyzed bicyclization.23-羟基十一烷基灵菌红素及其类似物的立体定向合成以及通过赖氏氧化酶催化的双环化反应转化为抗疟前海生菌素。
J Org Chem. 2014 Dec 5;79(23):11674-89. doi: 10.1021/jo5023553. Epub 2014 Nov 18.
本文引用的文献
1
Towards the Total Synthesis of Marineosin A: Construction of the Macrocyclic Pyrrole and an Advanced, Functionalized Spiroaminal Model.迈向海生素A的全合成：大环吡咯的构建及一个高级功能化螺胺模型
European J Org Chem. 2013 Jul 1;2013(20). doi: 10.1002/ejoc.201300643.
2
Spiroaminal Model Systems of the Marineosins with Final Step Pyrrole Incorporation.含最终步骤吡咯掺入的海洋菌素的螺胺模型系统。
Tetrahedron Lett. 2013 May 1;54(18):2231-2234. doi: 10.1016/j.tetlet.2013.02.059.
3
A concise approach to the spiroiminal fragment of marineosins.海洋奥辛斯螺环片段的简洁方法。
Org Biomol Chem. 2013 May 14;11(18):2936-8. doi: 10.1039/c3ob40208h.
4
Stereoselective synthesis of acortatarins A and B.阿科他他灵 A 和 B 的立体选择性合成。
Org Lett. 2012 Sep 7;14(17):4442-5. doi: 10.1021/ol3019456. Epub 2012 Aug 27.
5
Efficient synthesis of α-tertiary α-silylamines from aryl sulfonylimidates via one-pot, sequential C-Si/C-C bond formations.通过一锅法、顺序 C-Si/C-C 键形成反应，从芳基磺酰亚胺酯高效合成α-叔-α-硅基胺。
Org Lett. 2012 Jun 1;14(11):2906-9. doi: 10.1021/ol301194e. Epub 2012 May 23.
6
Total synthesis and biological evaluation of (-)-9-deoxy-englerin A.(-)-9-去氧埃格林 A 的全合成及生物评价。
Org Lett. 2011 Apr 15;13(8):2090-3. doi: 10.1021/ol200499t. Epub 2011 Mar 17.
7
Asymmetric conjugate silyl transfer in iterative catalytic sequences: synthesis of the C7-C16 fragment of (+)-neopeltolide.迭代催化序列中的不对称共轭硅基转移反应：（+）-新软海绵素C7-C16片段的合成
Angew Chem Int Ed Engl. 2010 Aug 16;49(35):6195-8. doi: 10.1002/anie.201002916.
8
An Alkoxide Anion Triggered tert-Butyloxycarbonyl Group Migration. Mechanism and Application.醇盐阴离子引发的叔丁氧羰基迁移：机理与应用
Tetrahedron Lett. 2010 May 5;51(18):2536-2538. doi: 10.1016/j.tetlet.2010.03.009.
9
Synthesis of the spiroiminal moiety of marineosins A and B.海洋奥辛 A 和 B 的螺环亚胺部分的合成。
Org Lett. 2010 Apr 2;12(7):1600-3. doi: 10.1021/ol100333d.
10
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.
Zotero 插件