Syntheses of Sceptrins and Nakamuric Acid and Insights into the Biosyntheses of Pyrrole-Imidazole Dimers

Organic Chemistry Frontiers : an International Journal of Organic Chemistry
Xiaolei WangChuo Chen

Abstract

Sceptrins and nakamuric acid are structurally unique antibiotics isolated from marine sponges. Recent studies suggest that the biosynthesis of these dimeric pyrrole-imidazole alkaloids involves a single-electron transfer (SET)-promoted [2+2] cycloaddition to form their cyclobutane core skeletons. We describe herein the biomimetic syntheses of racemic sceptrin and nakamuric acid. We also report the asymmetric syntheses of sceptrin, bromosceptrin, and dibromosceptrin in their natural enantiomeric form. We further provide mechanistic insights into the pathway selectivity of the SET-promoted [2+2] and [4+2] cycloadditions that lead to the divergent formation of the sceptrin and ageliferin core skeletons. Both the [2+2] and [4+2] cycloadditions are stepwise reactions, with the [2+2] pathway kinetically and thermodynamically favored over the [4+2] pathway. For the [2+2] cycloaddition, the dimerization of pyrrole-imidazole monomers is rate-limiting, whereas for the [4+2] cycloaddition, the cyclization is the slowest step.

References

Oct 9, 1999·Journal of Natural Products·C EderS Sudarsono
Apr 3, 2002·Zeitschrift Für Naturforschung. C, a Journal of Biosciences·Michael Assmann, Matthias Köck
Oct 31, 2002·Journal of the American Chemical Society·Neil K GargBrian M Stoltz
Mar 25, 2004·Journal of the American Chemical Society·Phil S BaranDaniel P O'Malley
Jul 2, 2004·Organic Letters·Vladimir B Birman, Xun-Tian Jiang
Aug 29, 2007·Angewandte Chemie·Matthias KöckPhil S Baran
Oct 10, 2007·Chirality·H D Flack, G Bernardinelli
May 31, 2008·Angewandte Chemie·Hans-Dieter Arndt, Matthias Riedrich
Sep 5, 2008·Journal of the American Chemical Society·Michael A IschayTehshik P Yoon
Feb 1, 2008·Journal of Applied Crystallography·Rob W W HooftAnthony L Spek
May 29, 2009·Journal of the American Chemical Society·Juana Du, Tehshik P Yoon
Dec 1, 2009·Angewandte Chemie·Kirsten Zeitler
Jan 26, 2010·Marine Drugs·Barbara ForteGianluca Papeo
Jun 10, 2010·Journal of the American Chemical Society·Michael A IschayTehshik P Yoon
Jun 10, 2010·Chemical Society Reviews·Jagan M R Narayanam, Corey R J Stephenson
Jun 24, 2010·Nature Chemistry·Tehshik P YoonJuana Du
Sep 18, 2010·Chemical Communications : Chem Comm·Zhiqiang MaChuo Chen
Sep 6, 2011·Journal of the American Chemical Society·Xiao WangChuo Chen
Oct 29, 2011·Journal of the American Chemical Society·Shishi LinTehshik P Yoon
Jan 31, 2012·The Journal of Organic Chemistry·Joseph W Tucker, Corey R J Stephenson
Feb 11, 2012·Organic Letters·Elizabeth L TysonTehshik P Yoon
Jun 20, 2012·Angewandte Chemie·Jun Xuan, Wen-Jing Xiao
Sep 12, 2012·Angewandte Chemie·Zhan Lu, Tehshik P Yoon
Sep 18, 2012·Chemical Science·Michael A IschayTehshik P Yoon
Mar 21, 2013·Chemical Reviews·Christopher K PrierDavid W C MacMillan
May 21, 2013·Chemical Science·Hui DingPatrick G Harran
Mar 1, 2014·Science·Danielle M Schultz, Tehshik P Yoon
May 16, 2014·Chemical Communications : Chem Comm·Xiao WangChuo Chen
Jul 6, 2014·Angewandte Chemie·Anna E HurtleyTehshik P Yoon
Feb 17, 2015·Tetrahedron·Yuyong MaChuo Chen
May 20, 2015·Tetrahedron·Xiaolei Wang, Chuo Chen

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Citations

Feb 6, 2016·Natural Product Reports·Yuanyou Qiu, Shuanhu Gao
Nov 24, 2017·Natural Product Reports·Wen-Ju Bai, Xiqing Wang
Feb 13, 2018·Journal of the Chinese Chemical Society·Zhiqiang Ma, Chuo Chen
Mar 9, 2021·Organic & Biomolecular Chemistry·Apsara K Herath, Carl J Lovely
Jul 8, 2021·Chemical Reviews·Spencer P Pitre, Larry E Overman
May 8, 2020·Organic Letters·Long V Nguyen, Timothy F Jamison

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