Regio- and Stereospecific 1,3-Allyl Group Transfer Triggered by a Copper-Catalyzed Borylation/ortho-Cyanation Cascade.
A copper-catalyzed borylation/ortho-cyanation/allyl group transfer cascade was developed. Initiated by an unconventional copper-catalyzed electrophilic dearomatization, this process features regio- and stereospecific 1,3-transposition of the allyl fragment enabled by an aromatization-driven Cope rearrangement. This method provides an effective means for the construction of adjacent tertiary and quaternary stereocenters with excellent diastereocontrol.
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139 (USA). yang89@mit.edu.
Yang
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Yang
D001897:Boronic Acids / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D015394:Molecular Structure; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism
D001897:Boronic Acids; D009570:Nitriles; D009942:Organometallic Compounds; D003300:Copper
CC activation; copper; cyanation; dearomatization; sigmatropic rearrangement