Catalytic SN2′- and Enantioselective Allylic Substitution with a Diborylmethane Reagent and Application in Synthesis
Ying Shi
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA, 02467 USA
Search for more papers by this authorCorresponding Author
Prof. Amir H. Hoveyda
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA, 02467 USA
Search for more papers by this authorYing Shi
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA, 02467 USA
Search for more papers by this authorCorresponding Author
Prof. Amir H. Hoveyda
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA, 02467 USA
Search for more papers by this authorAbstract
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 SN2′/SN2 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.
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