Regiochemical control in the metal-catalyzed transposition of allylic silyl ethers.
A novel mode of regiochemical control over the allylic [1,3]-transposition of silyloxy groups catalyzed by Re2O7 has been developed. This strategy relies on a cis-oriented vinyl boronate, generated from the Alder-ene reaction of homoallylic silyl ethers and alkynyl boronates, to trap out the allylic hydroxyl group. The resulting cyclic boronic acids are excellent partners for cross-coupling reactions. High chirality transfer is observed for the rearrangement of enantioenriched allylic silyl ethers.
Hansen
Eric C
EC
Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA.
Lee
Daesung
D
D001897:Boronic Acids / Q000138:chemical synthesis; D002384:Catalysis; D003500:Cyclization; D004987:Ethers / Q000737:chemistry*; D015394:Molecular Structure; D017646:Organosilicon Compounds / Q000737:chemistry*; D020005:Propanols / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000138:chemical synthesis
D001897:Boronic Acids; D004987:Ethers; D017646:Organosilicon Compounds; D020005:Propanols; D014753:Vinyl Compounds; C006463:allyl alcohol; D012211:Rhenium; D012428:Ruthenium