(-)-Psychotridine 的全合成与立体化学构型确定。
Total Synthesis and Stereochemical Assignment of (-)-Psychotridine.
机构信息
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
出版信息
Org Lett. 2022 Mar 25;24(11):2160-2164. doi: 10.1021/acs.orglett.2c00448. Epub 2022 Mar 17.
Abstract
We report the first enantioselective total synthesis and stereochemical assignment of (-)-psychotridine. The application of our diazene-directed assembly of enantiomerically enriched cyclotryptamines afforded a highly convergent synthesis of the pentameric alkaloid, allowing its detailed structural assignment. Highlights of the synthesis include the introduction of four quaternary stereocenters with complete stereochemical control in a single step via the photoextrusion of three molecules of dinitrogen from an advanced intermediate and metal-catalyzed C-H amination reactions in challenging settings.
摘要
我们报告了 (-)-psychotridine 的首次对映选择性全合成和立体化学构型确定。我们的 diazene 导向的手性富集环色胺组装方法应用于五聚体生物碱的高度汇聚合成，从而能够对其进行详细的结构确定。该合成的亮点包括通过从一个先进的中间体中光解三个氮气分子一步引入四个四级立体中心，并在具有挑战性的条件下通过金属催化的 C-H 胺化反应实现完全立体化学控制。
相似文献
1
Total Synthesis and Stereochemical Assignment of (-)-Psychotridine.
Org Lett. 2022 Mar 25;24(11):2160-2164. doi: 10.1021/acs.orglett.2c00448. Epub 2022 Mar 17.
2
Concise Synthesis of (-)-Hodgkinsine, (-)-Calycosidine, (-)-Hodgkinsine B, (-)-Quadrigemine C, and (-)-Psycholeine via Convergent and Directed Modular Assembly of Cyclotryptamines.
J Am Chem Soc. 2017 Dec 6;139(48):17590-17596. doi: 10.1021/jacs.7b09929. Epub 2017 Nov 20.
3
Unified, Biosynthesis-Inspired, Completely Stereocontrolled Total Synthesis of All Highest-Order [n + 1] Oligocyclotryptamine Alkaloids.
J Am Chem Soc. 2024 Aug 21;146(33):23574-23581. doi: 10.1021/jacs.4c07705. Epub 2024 Aug 12.
4
Highly enantioselective organocatalytic α-amination reactions of aryl oxindoles: developing designer multifunctional alkaloid catalysts.
Org Lett. 2010 Dec 17;12(24):5696-9. doi: 10.1021/ol102493q. Epub 2010 Nov 11.
5
Convergent and Biomimetic Enantioselective Total Synthesis of (-)-Communesin F.
J Am Chem Soc. 2016 Jun 22;138(24):7763-9. doi: 10.1021/jacs.6b04072. Epub 2016 Jun 14.
6
Application of diazene-directed fragment assembly to the total synthesis and stereochemical assignment of (+)-desmethyl--chimonanthine and related heterodimeric alkaloids.
Chem Sci. 2014 Jan 1;5(1). doi: 10.1039/C3SC52451E.
7
Intramolecular dearomative oxidative coupling of indoles: a unified strategy for the total synthesis of indoline alkaloids.
Acc Chem Res. 2015 Mar 17;48(3):702-11. doi: 10.1021/ar5004303. Epub 2015 Feb 10.
8
Concise Enantioselective Total Synthesis of Daphenylline Enabled by an Intramolecular Oxidative Dearomatization.
J Am Chem Soc. 2022 Apr 6;144(13):5750-5755. doi: 10.1021/jacs.2c01674. Epub 2022 Mar 15.
9
An enantioselective total synthesis and stereochemical revision of (+)-citrinadin B.
J Am Chem Soc. 2013 Jul 31;135(30):10890-3. doi: 10.1021/ja405548b. Epub 2013 Jul 18.
10
Enantioselective Synthesis of 3-Substituted 3-Amino-2-oxindoles by Amination with Anilines.
Chemistry. 2021 Jun 25;27(36):9272-9275. doi: 10.1002/chem.202100829. Epub 2021 May 28.
引用本文的文献
1
Catalytic diazene synthesis from sterically hindered amines for deaminative functionalization.
Nat Commun. 2025 Jul 7;16(1):6266. doi: 10.1038/s41467-025-61662-9.
2
Photochemical Homodimerization as a Key Step in Natural Product Synthesis.
Tetrahedron. 2025 Sep 1;183. doi: 10.1016/j.tet.2025.134706. Epub 2025 May 8.
3
Unified, Biosynthesis-Inspired, Completely Stereocontrolled Total Synthesis of All Highest-Order [n + 1] Oligocyclotryptamine Alkaloids.
J Am Chem Soc. 2024 Aug 21;146(33):23574-23581. doi: 10.1021/jacs.4c07705. Epub 2024 Aug 12.
本文引用的文献
1
Total Synthesis and Anti-Cancer Activity of All Known Communesin Alkaloids and Related Derivatives.
J Am Chem Soc. 2019 Sep 11;141(36):14411-14420. doi: 10.1021/jacs.9b07397. Epub 2019 Aug 30.
2
Catalyst-controlled oligomerization for the collective synthesis of polypyrroloindoline natural products.
Nat Chem. 2017 Dec;9(12):1165-1169. doi: 10.1038/nchem.2825. Epub 2017 Jul 24.
3
Concise Synthesis of (-)-Hodgkinsine, (-)-Calycosidine, (-)-Hodgkinsine B, (-)-Quadrigemine C, and (-)-Psycholeine via Convergent and Directed Modular Assembly of Cyclotryptamines.
J Am Chem Soc. 2017 Dec 6;139(48):17590-17596. doi: 10.1021/jacs.7b09929. Epub 2017 Nov 20.
4
Iridium(III)-Catalyzed Regioselective C7-Amination of N-Pivaloylindoles with Sulfonoazides.
J Org Chem. 2016 Nov 4;81(21):10476-10483. doi: 10.1021/acs.joc.6b01856. Epub 2016 Sep 13.
5
Convergent and Biomimetic Enantioselective Total Synthesis of (-)-Communesin F.
J Am Chem Soc. 2016 Jun 22;138(24):7763-9. doi: 10.1021/jacs.6b04072. Epub 2016 Jun 14.
6
Synthetic Strategies toward Natural Products Containing Contiguous Stereogenic Quaternary Carbon Atoms.
Angew Chem Int Ed Engl. 2016 Mar 18;55(13):4156-86. doi: 10.1002/anie.201507549. Epub 2016 Feb 2.
7
Stereocontrolled enantioselective total synthesis of the [2+2] quadrigemine alkaloids.
Tetrahedron. 2015 Sep 16;71(37):6424-6436. doi: 10.1016/j.tet.2015.02.080.
8
Application of diazene-directed fragment assembly to the total synthesis and stereochemical assignment of (+)-desmethyl--chimonanthine and related heterodimeric alkaloids.
Chem Sci. 2014 Jan 1;5(1). doi: 10.1039/C3SC52451E.
9
Selective intermolecular amination of C-H bonds at tertiary carbon centers.
Angew Chem Int Ed Engl. 2013 Oct 18;52(43):11343-6. doi: 10.1002/anie.201304238. Epub 2013 Sep 2.
10
Catalytic enantioselective total synthesis of hodgkinsine B.
Angew Chem Int Ed Engl. 2011 Sep 19;50(39):9116-9. doi: 10.1002/anie.201103864. Epub 2011 Aug 24.
Zotero 插件