A general and regioselective synthesis of cyclopentenone derivatives through nickel(0)-mediated [3 + 2] cyclization of alkenyl Fischer carbene complexes and internal alkynes.
A broad range of substituted 2-cyclopentenone derivatives 3-6 are synthesized by the nickel(0)-mediated [3 + 2] cyclization reaction of chromium alkenyl(methoxy)carbene complexes 1 and internal alkynes 2. The reaction takes place with complete regioselectivity with both unactivated alkynes and activated alkynes (electron-withdrawing and electron-donating substituted alkynes). Representative cycloadducts containing boron and tin substituents are further demonstrated to be active partners in classical Pd-catalyzed C-C coupling processes to allow the production of 2-aryl- and 2-alkynyl-substituted cyclopentenones 9-13.
Barluenga
José
J
Instituto Universitario de Química Organometálica Enrique Moles, Unidad Asociada al CSIC, Universidad de Oviedo, Oviedo, Spain. barluenga@uniovi.es
Barrio
Pablo
P
Riesgo
Lorena
L
López
Luis A
LA
Tomás
Miguel
M
D000475:Alkenes / Q000737:chemistry*; D000480:Alkynes / Q000737:chemistry*; D001895:Boron / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D003517:Cyclopentanes / Q000138:chemical synthesis*; D006838:Hydrocarbons / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008956:Models, Chemical; D009532:Nickel / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry; D013237:Stereoisomerism
D000475:Alkenes; D000480:Alkynes; D003517:Cyclopentanes; D006838:Hydrocarbons; C030011:carbene; D010165:Palladium; D009532:Nickel; D001895:Boron; D008697:Methane; C013905:cyclopentenone