title: Catalytic SN2'- and Enantioselective Allylic Substitution with a Diborylmethane Reagent and Application in Synthesis.
abstract: A catalytic method for the site- and enantioselective addition of commercially available di-B(pin)-methane to allylic phosphates is introduced (pin=pinacolato). Transformations may be facilitated by an NHC-Cu complex (NHC=N-heterocyclic carbene) and products obtained in 63-95 % yield, 88:12 to >98:2 S(N)2'/S(N)2 selectivity, and 85:15-99:1 enantiomeric ratio. The utility of the approach, entailing the involvement of different catalytic cross-coupling processes, is highlighted by its application to the formal synthesis of the cytotoxic natural product rhopaloic acid A.
authors: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA, 02467, USA.
authors: Ying
authors: Y
authors: Shi
authors: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA, 02467, USA. amir.hoveyda@bc.edu.
authors: Amir H
authors: AH
authors: Hoveyda
mesh_terms: D001896:Boron Compounds / Q000737:chemistry*; D002384:Catalysis; D007202:Indicators and Reagents / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D001896:Boron Compounds; D007202:Indicators and Reagents
keywords: N-heterocyclic carbenes; allylic substitution; boron; copper; enantioselective synthesis