Macrocyclization by Nickel-Catalyzed, Ester-Promoted, Epoxide–Alkyne Reductive Coupling: Total Synthesis of (−)-Gloeosporone†
James D. Trenkle Dr.
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139 (USA), Fax: (+1) 617-324-0253 http://web.mit.edu/chemistry/jamison
Current address: Gilead Sciences, 333 Lakeside Dr., Foster City, CA 94404 (USA)
Search for more papers by this authorTimothy F. Jamison Prof. Dr.
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139 (USA), Fax: (+1) 617-324-0253 http://web.mit.edu/chemistry/jamison
Search for more papers by this authorJames D. Trenkle Dr.
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139 (USA), Fax: (+1) 617-324-0253 http://web.mit.edu/chemistry/jamison
Current address: Gilead Sciences, 333 Lakeside Dr., Foster City, CA 94404 (USA)
Search for more papers by this authorTimothy F. Jamison Prof. Dr.
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139 (USA), Fax: (+1) 617-324-0253 http://web.mit.edu/chemistry/jamison
Search for more papers by this authorSupport for this work was provided by the National Institute of General Medical Sciences (GM-72566). We are grateful to Li Li for obtaining mass spectrometric data for all compounds (MIT Department of Chemistry Instrumentation Facility, which is supported in part by the NSF (CHE-9809061 and DBI-9729592) and the NIH (1S10RR13886-01)).
Abstract
Im Zentrum der Totalsynthese der Titelverbindung steht eine neuartige Strategie, bei der mithilfe von Triethylboran und einem Nickel(0)-Phosphan-Komplex effizient ein 14-gliedriger Ring geschlossen wird (siehe Schema; cod=Cyclooctadien). Die Synthese verläuft über zehn Stufen in ca. 9 % Gesamtausbeute.
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