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Acta Chimica Sinica >

2017 , Vol. 75 >Issue 8: 798 - 807

DOI: https://doi.org/10.6023/A17040190

Article

Asymmetric Formal Synthesis of Cortistatins via a Gold-Catalyzed Semi-Pinacol Rearrangement Strategy

  • Gu Yueqing ,
  • Yuan Hao ,
  • Fu Junkai ,
  • Gong Jianxian ,
  • Yang Zhen
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  • a Laboratory of Chemical Genomics, School of Chemical Biology and Biotechnology, Peking University Shenzhen Graduate School, Shenzhen 518055, China;
    b Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University, Changchun 130024, China;
    c Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Beijing National Laboratory for Molecular Science, College of Chemistry and Molecular Engineering, and Peking-Tsinghua Center for Life Sciences, Peking University, Beijing 100871, China

Received date: 2017-04-28

  Online published: 2017-06-08

Supported by

Project supported by the National Natural Science Foundation of China (Nos.21372016,21572009 and 21632002).

Fold

Abstract

Over the past decade, Gold complexes have emerged as efficient and mild catalysts for the transformation of substrates possessing alkyne functionality into a range of useful scaffolds. These powerful methods have enabled the development of novel approaches for the total synthesis of biologically active natural products by gold catalysis. In this case, we found that the intramolecular nucleophilic addition of a hydroxyl group to a carbon-carbon triple bond, which activated by a gold catalyst, followed by further useful transformation has proven to be an excellent method for rapid construction of structural diversity of molecular scaffolds. The cortistatins are a family of 11 steroidal alkaloids which exhibit significant biological activities. The intriguing biological properties and their low natural abundance have elevated cortistatins to be a typical target for both partial and total synthesis. Up to now, more than a dozen research groups have published approaches directed toward the synthesis of cortistatins, including one semi-synthesis, five total syntheses and five formal syntheses, as well as a number of synthetic studies about the pentacyclic core and some illuminating model studies. One of the biggest challenges for the synthesis of cortistatins is how to construct the unprecedented oxabicyclo[3.2.1]octane ring system which lies within a complex tetracarbocyclic skeleton. In our previous work, we have developed a gold-catalyzed semi-pinacol rearrangement strategy to diastereoselective synthesis of the oxabicyclo[3.2.1]octane ring system. The wide substrate scope as well as the high diastereoselectivity have made us to apply this method into the asymmetric formal synthesis of Cortistatins. Herein, full details about our efforts towards the formal synthesis of cortistatins were described by employing our developed gold-catalyzed cascade reaction to oxabicyclo[3.2.1]octane ring systems. This route is featured with a novel gold-catalyzed cascade reaction involving intramolecular nucleophilic addition of hydroxyl group to the carbon-carbon triple bond, followed by an oxonium ion initiated semi-pinacol-type 1,2-migration to construct the key oxabicyclo[3.2.1]octane skeleton.

Key words： gold catalysis; oxabicyclo[3.2.1]octane skeletons; formal synthesis; semi-pinacol rearrangement; Cortistatins

Cite this article

Gu Yueqing , Yuan Hao , Fu Junkai , Gong Jianxian , Yang Zhen . Asymmetric Formal Synthesis of Cortistatins via a Gold-Catalyzed Semi-Pinacol Rearrangement Strategy[J]. Acta Chimica Sinica, 2017 , 75(8) : 798 -807 . DOI: 10.6023/A17040190

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