Asymmetric Total Synthesis of (-)-Englerin A through Catalytic Diastereo- and Enantioselective Carbonyl Ylide Cycloaddition.

Abstract

An asymmetric total synthesis of the guaiane sesquiterpene (-)-englerin A, a potent and selective inhibitor of the growth of renal cancer cell lines, was accomplished. The basis of the approach is a highly diastereo- and enantioselective carbonyl ylide cycloaddition with an ethyl vinyl ether dipolarophile under catalysis by dirhodium(II) tetrakis[N-tetrachlorophthaloyl-(S)-tert-leucinate], [Rh2 (S-TCPTTL)4 ], to construct the oxabicyclo[3.2.1]octane framework with concomitant introduction of the oxygen substituent at C9 on the exo-face. Another notable feature of the synthesis is ruthenium tetraoxide-catalyzed chemoselective oxidative conversion of C9 ethyl ether to C9 acetate.

• Authors: Taiki Hanari, Naoyuki Shimada, Yasunobu Kurosaki, Neetipalli Thrimurtulu, Hisanori Nambu, Masahiro Anada, Shunichi Hashimoto
• Journal: Chemistry (Weinheim an der Bergstrasse, Germany) (Chemistry) Vol. 21 Issue 33 Pg. 11671-6 (Aug 10 2015) ISSN: 1521-3765 [Electronic] Germany
• PMID: 26179743 (Publication Type: Journal Article, Research Support, Non-U.S. Gov't)
• Copyright: © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical References

• Antineoplastic Agents
• Biological Factors
• Coordination Complexes
• Ethyl Ethers
• Sesquiterpenes, Guaiane
• dirhodium(II) tetrakis(N-tetrachlorophthaloyl-(S)-tert-leucinate)
• englerin A
• Rhodium

Topics

• Antineoplastic Agents (chemical synthesis, chemistry, pharmacology)
• Biological Factors (chemistry)
• Catalysis
• Cell Line, Tumor
• Coordination Complexes (chemistry)
• Cycloaddition Reaction
• Ethyl Ethers (chemistry)
• Humans
• Kidney Neoplasms (chemistry, pathology)
• Molecular Structure
• Rhodium (chemistry)
• Sesquiterpenes, Guaiane (chemical synthesis, chemistry)
• Stereoisomerism