Synthetic Studies on Enantioselective Total Synthesis of Cyathane Diterpenoids: Cyrneines A and B, Glaucopine C, and (+)-Allocyathin B2

The Journal of Organic Chemistry
Guo-Jie WuFu-She Han

Abstract

The details for the synthetic studies on enantioselective total synthesis of cyathane diterpenoids cyrneine A (1) and B (2), glaucopine C (3), and (+)-allocyathin B2 are presented. We established a mild Suzuki coupling for heavily substituted nonactivated cyclopentenyl triflates using a phosphinamide-derived palladacycle as precatalyst and a chelation-controlled highly regioselective Friedel-Crafts cyclization. The utilization of these two key reactions enabled a rapid construction of the 5-6-6 tricyclic skeleton. In the middle stage of the synthesis, a Birch reductive methylation, a modified Wolff-Kishner-Huang reduction, and a carbenoid-mediated ring expansion were employed as the key reactions to furnish the 5-6-7 tricyclic core bearing two antiorientated all-carbon quaternary stereocenters at the C6 and C9 ring junctions. By applying these key transformations, a more efficient total synthesis of cyrneine A and allocyathin B2, and the first total synthesis of cyrneine B and glaucopine C, were accomplished through a collective manner. The late-stage conversions involving a base-mediated double bond migration and a double bond migration/aerobic γ-CH oxidation cascade for the stereoselective synthesis of cyrneine B and glaucopi...Continue Reading

References

Feb 11, 1999·Bioscience, Biotechnology, and Biochemistry·H ShibataY Morita
May 18, 2000·Organic Letters·E PiersK L Cook
Feb 24, 2001·Bioscience, Biotechnology, and Biochemistry·E W LeeH Kawagish
May 15, 2002·Bioscience, Biotechnology, and Biochemistry·Hiromichi KenmokuTakeshi Sassa
Jul 19, 2002·Chemical Communications : Chem Comm·Michael C WillisMary F Mahon
Jun 25, 2004·Bioscience, Biotechnology, and Biochemistry·Tsunashi KamoMitsuru Hirota
Dec 21, 2004·Organic Letters·Masashi TakanoMasahisa Nakada
Dec 22, 2004·Chemistry : a European Journal·Barry M TrostIrwin Chen
Mar 3, 2005·Journal of the American Chemical Society·Barry M TrostGretchen M Schroeder
Apr 14, 2005·Journal of the American Chemical Society·Matthew W B Pfeiffer, Andrew J Phillips
Jul 20, 2005·Journal of Basic Microbiology·Bing-Ji Ma, Ji-Kai Liu
Jul 21, 2005·Journal of the American Chemical Society·Barry M TrostGretchen M Schroeder
Aug 27, 2005·The Journal of Organic Chemistry·Ernesto G OcchiatoAntonio Guarna
Sep 30, 2005·Journal of the American Chemical Society·Stephen P WatersSamuel J Danishefsky
May 27, 2006·Journal of Natural Products·Jiangnan PengMark T Hamann
Jul 21, 2006·Natural Product Research·Maria Carla MarcotullioAurelia Tubaro
Aug 2, 2006·Planta medica·Maria Carla MarcotullioMassimo Curini
Oct 13, 2006·Organic & Biomolecular Chemistry·Duanpen Lertpibulpanya, Stephen P Marsden
Nov 17, 2006·Organic Letters·T Jagadeeswar ReddyLaird Trimble
Feb 27, 2007·Bioorganic & Medicinal Chemistry·Maria Carla MarcotullioNorimichi Nakahata
May 15, 2007·The Journal of Organic Chemistry·Weimin Lin, Charles K Zercher
Jun 22, 2007·Organic Letters·Dale E Ward, Jianheng Shen
Apr 15, 2008·The Journal of Antibiotics·Bing-Ji Ma, Yuan Ruan
Apr 24, 2009·Natural Product Reports·John A Enquist, Brian M Stoltz
Jun 23, 2009·Angewandte Chemie·Keunho Kim, Jin Kun Cha
May 26, 2010·Organic & Biomolecular Chemistry·Corinne BaumgartnerBrian M Stoltz
May 3, 2011·European Journal of Medicinal Chemistry·Xin-Wei ShiAn-Ling Zhang
Mar 21, 2012·Angewandte Chemie·Elangovan ElamparuthiKarl Gademann
Feb 6, 2013·Organic Letters·Biao JiangZuo-Gang Huang
Aug 30, 2013·The Journal of Organic Chemistry·Prithiba MitraDipakranjan Mal
Jul 30, 2014·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Masahisa Nakada

❮ Previous
Next ❯

Citations

Jan 28, 2020·Chemical Communications : Chem Comm·Abigail R HanbyDavid R Spring
Jun 3, 2020·Pharmacological Research : the Official Journal of the Italian Pharmacological Society·Christian Bailly, Jin-Ming Gao
Mar 28, 2020·The Journal of Organic Chemistry·Yulong LiZhi-Xiang Xie

❮ 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.