The regio- and stereospecific intermolecular dehydrative alkoxylation of allylic alcohols catalyzed by a gold(I) N-heterocyclic carbene complex.
A 1:1 mixture of [AuCl(IPr)] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidine) and AgClO(4) catalyzes the intermolecular dehydrative alkoxylation of primary and secondary allylic alcohols with aliphatic primary and secondary alcohols to form allylic ethers. These transformations are regio- and stereospecific with preferential addition of the alcohol nucleophile at the γ-position of the allylic alcohol syn to the departing hydroxyl group and with predominant formation of the E stereoisomer. The minor α regioisomer is formed predominantly through a secondary reaction manifold involving regioselective γ-alkoxylation of the initially formed allylic ether rather than by the direct α-alkoxylation of the allylic alcohol.
Department of Chemistry, Duke University, French Family Science Center, Durham, NC 27708, USA.
Paramita
P
Mukherjee
Ross A
RA
Widenhoefer
D000498:Allyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D004987:Ethers / Q000138:chemical synthesis* / Q000737:chemistry; D006046:Gold / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D015394:Molecular Structure; D020005:Propanols / Q000737:chemistry*; D013237:Stereoisomerism
D000498:Allyl Compounds; D004987:Ethers; D020005:Propanols; C030011:carbene; C006463:allyl alcohol; D006046:Gold; D008697:Methane