Phosphine-catalyzed regiospecific allylic amination and dynamic kinetic resolution of Morita-Baylis-Hillman acetates.
Exposure of Morita-Baylis-Hillman (MBH) acetates to tertiary phosphine catalysts in the presence of 4,5-dichlorophthalimide enables regiospecific allylic substitution through a tandem S(N)2'-S(N)2' mechanism. Through the use of the chiral phosphine catalyst (R)-Cl-MeO-BIPHEP, chiral racemic MBH acetate 4 is converted to the corresponding allylic amination product in 80% yield and 56% enantiomeric excess, thus establishing the feasibility of dynamic kinetic resolution. [reaction: see text]
Cho
Chang-Woo
CW
Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, TX 78712, USA.
Kong
Jong-Rock
JR
Krische
Michael J
MJ
D000085:Acetates / Q000737:chemistry*; D000478:Alkylation; D000498:Allyl Compounds / Q000737:chemistry*; D000586:Amination; D002384:Catalysis; D007700:Kinetics; D015394:Molecular Structure; D010720:Phosphines / Q000737:chemistry*; D013237:Stereoisomerism
D000085:Acetates; D000498:Allyl Compounds; D010720:Phosphines; C044646:phosphine