Tandem Pd(II)-catalyzed vinyl ether exchange-Claisen rearrangement as a facile approach to gamma,delta-unsaturated aldehydes.
A sequential allyl vinyl ether formation-Claisen rearrangement process catalyzed by a palladium(II)-phenanthroline complex is reported. The effects of allylic alcohol structure, type of vinylating agent, and palladium catalysts are discussed. This method provides a convenient approach to gamma,delta-unsaturated aldehydes under mild conditions that avoid the use of toxic Hg(II) catalysts. The new methodology has been successfully demonstrated on the kilogram scale.
Wei
Xudong
X
Department of Chemical Development, Boehringer Ingelheim Pharmaceuticals, Inc., 900 Ridgebury Road, Ridgefield, Connecticut 06877, USA. xwei@rdg.boehringer-ingelheim.com
Lorenz
Jon C
JC
Kapadia
Suresh
S
Saha
Anjan
A
Haddad
Nizar
N
Busacca
Carl A
CA
Senanayake
Chris H
CH
D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D010165:Palladium / Q000737:chemistry*; D010618:Phenanthrolines / Q000737:chemistry*; D020005:Propanols / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics; D014753:Vinyl Compounds / Q000737:chemistry*
D000447:Aldehydes; D010618:Phenanthrolines; D020005:Propanols; D014753:Vinyl Compounds; C100195:vinyl ether; C006463:allyl alcohol; D010165:Palladium