Nickel-catalyzed reductive coupling of alkynes and epoxides.
Nickel-catalyzed, intramolecular and intermolecular reductive coupling of alkynes and epoxides affords synthetically useful homoallylic alcohols of defined alkene geometry. Very high regioselectivity is generally observed, and cyclizations proceed with complete selectivity for endo epoxide opening. This catalytic reaction represents the first use of a non-pi-based electrophile in a growing class of nickel-catalyzed, multicomponent coupling reactions, and is the first catalytic method of reductive coupling of alkynes and epoxides that is effective for both intermolecular and intramolecular cases, and mechanistically distinct from these, possibly involving a nickella(II)oxetane.
Molinaro
Carmela
C
Massachusetts Institute of Technology, Department of Chemistry, Cambridge, MA 02139, USA.
Jamison
Timothy F
TF
D000438:Alcohols / Q000138:chemical synthesis*; D000475:Alkenes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D002384:Catalysis; D004852:Epoxy Compounds / Q000737:chemistry*; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry
D000438:Alcohols; D000475:Alkenes; D000480:Alkynes; D004852:Epoxy Compounds; D009942:Organometallic Compounds; D009532:Nickel