Eta3-pyranyl and eta3-pyridinyl molybdenum pi-complexes as chiral scaffolds for the enantioselective construction of substituted oxa- and aza[3.3.1]bicyclics: first enantio- and regiocontrolled [5+3] cycloaddition reactions.
The first Mo-mediated [5+3] cycloadditions are reported. 3-Substituted pyranyl and pyridinyl molybdenum pi-complexes participate in enantiocontrolled [5+3] cycloadditions and provide a new and efficient synthetic approach to oxa- and aza[3.3.1]bicyclics of high enantiomeric purity. The reaction proceeds in good to excellent yields and with complete regio- and endo-selectivities; it diverts to a [2+3] cycloaddition pathway when 2-substituted heterocycle pi-complexes are used. This methodology, coupled with a variety of general demetalation protocols, holds much promise in synthetic applications.
Arrayás
Ramón Gómez
RG
Department of Chemistry, Emory University, 1515 Pierce Drive, Atlanta, GA 30322, USA.
Liebeskind
Lanny S
LS
D001372:Aza Compounds / Q000138:chemical synthesis*; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis*; D003500:Cyclization; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry; D011714:Pyrans / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D013237:Stereoisomerism
D001372:Aza Compounds; D001643:Bridged Bicyclo Compounds; D009942:Organometallic Compounds; D011714:Pyrans; D011725:Pyridines; D008982:Molybdenum