Total Syntheses of Echitamine, Akuammiline, Rhazicine, and Pseudoakuammigine

Angewandte Chemie
Xiang ZhangAng Li

Abstract

Echitamine (1) and akuammiline (2) are representative members of a fascinating class of monoterpenoid indole alkaloids. We report the syntheses of 2 and its congener deacetylakuammiline (3). The azabicyclo[3.3.1]nonane motif was assembled through silver-catalyzed internal alkyne cyclization, and one-pot C-O bond cleavage/C-N bond formation furnished the pentacyclic scaffold. Compound 3 then served as a common intermediate for preparing a series of structurally diverse and synthetically challenging congeners including 1. A position-selective Polonovski-Potier reaction followed by formal N-4 migration built the core of N-demethylechitamine (4) and 1. An alternative route featuring Meisenheimer rearrangement gave 4 as well. Oxidation of the alcohol within 3 gave rhazimal (5), which underwent tandem indolenine hydrolysis, hemiaminalization, and hemiketalization to form rhazicine (6). A sequence of N,O-ketalization and reductive amination secured the chemoselectivity of N-methylation, leading to pseudoakuammigine (7).

References

Jun 1, 1976·Planta medica·W Boonchuay, W E Court
Oct 9, 1965·British Medical Journal·L Brain
Jul 23, 2003·Current Medicinal Chemistry·Antonio Ramírez, Silvina García-Rubio
Jan 30, 2004·Journal of the American Chemical Society·Elizabeth A ColbyTimothy F Jamison
Nov 6, 2004·The Journal of Organic Chemistry·Charles DidierAnthony G M Barrett
Nov 16, 2004·Chemical Communications : Chem Comm·Dirk SchwaebischJack E Baldwin
Oct 1, 1989·Planta medica·W L HuM Hesse
Feb 29, 2008·Journal of the American Chemical Society·Amy B DounayAaron D Wrobleski
Mar 31, 2009·Journal of the American Chemical Society·Min ZhangYong Qin
Apr 16, 2011·Accounts of Chemical Research·Dan ZhangYong Qin
May 11, 2011·Journal of the American Chemical Society·Liansuo ZuNeil K Garg
Jul 15, 2011·Nature·Spencer B JonesDavid W C MacMillan
Jan 28, 2012·Journal of the American Chemical Society·Gregory L AdamsAmos B Smith
May 24, 2012·Journal of the American Chemical Society·Weiwei ZiDawei Ma
Nov 22, 2012·Angewandte Chemie·Hao WeiChuang-chuang Li
Dec 28, 2012·Journal of the American Chemical Society·Gregory L AdamsAmos B Smith
Apr 17, 2013·Journal of the American Chemical Society·Benjamin D Horning, David W C MacMillan
Jul 25, 2013·Nature Chemistry·Zhaoyong LuAng Li
Aug 24, 2013·Journal of the American Chemical Society·Myles W Smith, Scott A Snyder
Jan 24, 2014·Angewandte Chemie·Weiwu RenJieping Zhu
Feb 1, 2014·Angewandte Chemie·Mingxing TengDawei Ma
Mar 7, 2014·Journal of the American Chemical Society·Joel M SmithNeil K Garg
Oct 28, 2014·Angewandte Chemie·Joel M SmithNeil K Garg
Jul 3, 2015·The Journal of Organic Chemistry·Joel M SmithNeil K Garg
Feb 5, 2016·Angewandte Chemie·Weiwu RenJieping Zhu
Mar 11, 2016·Journal of the American Chemical Society·Yong LiAng Li
Mar 24, 2016·Angewandte Chemie·Clément F HeinrichLaurence Miesch
Mar 25, 2016·Organic Letters·Daisuke NishiyamaHiroaki Ohno
Jun 14, 2016·Angewandte Chemie·Guang LiLiansuo Zu
Jan 11, 2017·Chemistry : a European Journal·Ruben EckermannTanja Gaich
Feb 1, 2017·BJOG : an International Journal of Obstetrics and Gynaecology·E T Jensen
Mar 24, 2017·Organic Letters·Taimin WangHongbin Zhai
Mar 31, 2017·Organic Letters·Dan WangShuanhu Gao
May 4, 2017·Angewandte Chemie·Benxiang ZhangChaozhong Li
Sep 28, 2017·Organic Letters·Xiaoni XieLiansuo Zu
Sep 29, 2017·Journal of the American Chemical Society·Jian LiAng Li
Nov 24, 2017·Chemical Communications : Chem Comm·Tao XiaoYong Qin
Mar 2, 2018·Journal of the American Chemical Society·Wenhao ZhangAng Li
Apr 26, 2018·Journal of the American Chemical Society·Elias PicazoNeil K Garg
May 4, 2018·Fitoterapia·Abrar AhmedSheng Yin

❮ Previous
Next ❯

Citations

Feb 12, 2020·Angewandte Chemie·Sanghyeon LeeSunkyu Han
Apr 9, 2019·Angewandte Chemie·Yuye ChenJing Xu
Mar 30, 2021·Angewandte Chemie·Feng-Yuan Wang, Lei Jiao
Apr 29, 2021·Organic & Biomolecular Chemistry·Hiroaki Ohno, Shinsuke Inuki
Nov 20, 2019·Chemical Science·Haiyong YuTao Xu
Apr 25, 2019·Journal of the American Chemical Society·Zhiyao ZhouScott A Snyder
Jul 3, 2019·Accounts of Chemical Research·Xiao-Yu Liu, Yong Qin
Jan 30, 2020·Journal of the American Chemical Society·Benxiang ZhangChaozhong Li
Jan 16, 2020·Organic Letters·James A Rossi-AshtonWilliam P Unsworth
May 30, 2019·Organic Letters·Yuye ChenJing Xu
Nov 7, 2019·Journal of Natural Products·Guoqing ChenChenze Qi

❮ Previous
Next ❯

Related Concepts

Related Feeds

Cell Migration

Cell migration is involved in a variety of physiological and pathological processes such as embryonic development, cancer metastasis, blood vessel formation and remoulding, tissue regeneration, immune surveillance and inflammation. Here is the latest research.

Related Papers

Yakugaku zasshi : Journal of the Pharmaceutical Society of Japan
T Naito
Journal of the American Chemical Society
Ming BianAng Li
The Journal of Organic Chemistry
J D ALBRIGHT, L GOLDMAN
© 2022 Meta ULC. All rights reserved