Macrocyclization by nickel-catalyzed, ester-promoted, epoxide-alkyne reductive coupling: total synthesis of (-)-gloeosporone.
Ringing the changes: The total synthesis of the title compound centers around a novel strategy that employs a nickel(0)-phosphine complex and triethyl borane in an efficient closure of a 14-membered ring through C--C bond formation (see scheme; cod=cyclooctadiene). The synthesis was accomplished in 10 steps and in approximately 9 % overall yield.
Trenkle
James D
JD
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
Jamison
Timothy F
TF
D000480:Alkynes / Q000737:chemistry*; D001880:Boranes / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D004852:Epoxy Compounds / Q000737:chemistry*; D007783:Lactones / Q000138:chemical synthesis*; D009532:Nickel / Q000737:chemistry*; D010084:Oxidation-Reduction; D010720:Phosphines / Q000737:chemistry; D013237:Stereoisomerism
D000480:Alkynes; D001880:Boranes; D004852:Epoxy Compounds; D007783:Lactones; D010720:Phosphines; C484172:gloeosporone; D009532:Nickel; C044646:phosphine; C079756:triethylborane