Carbolithiation for the generation of cyclooctadienyl anions and tandem electrocyclization/alkylation to functionalized cis-bicyclo[3.3.0]octenes.
A powerful cascade reaction process for the construction of functionalized cis-bicyclo[3.3.0]octenes has been developed. Carbolithiation of 3-methylene-1,4-cyclooctadiene with 1 degrees , 2 degrees , or 3 degrees alkyllithium reagents leads to cyclooctadienyl anions, which undergo disrotatory electrocyclization and subsequent trapping with carbon, oxygen, sulfur, or silicon electrophiles to provide functionalized cis-bicyclo[3.3.0]octenes. Transmetalation of the allyllithium intermediates allowed access to the cuprate manifold of reactivity. The rapid construction of a linear triquinane using this methodology demonstrates the potential for synthetic applications.
Williams
David R
DR
Department of Chemistry, Indiana University, Bloomington, Indiana 47405-7102, USA. williamd@indiana.edu
Reeves
Jonathan T
JT
D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D000478:Alkylation; D000838:Anions / Q000737:chemistry; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D003500:Cyclization; D004563:Electrochemistry; D008094:Lithium / Q000737:chemistry*; D009795:Octanes / Q000138:chemical synthesis* / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry
D000475:Alkenes; D000838:Anions; D001643:Bridged Bicyclo Compounds; D009795:Octanes; D009942:Organometallic Compounds; D008094:Lithium