Pd asymmetric allylic alkylation (AAA). A powerful synthetic tool.
Palladium catalyzed asymmetric allylic alkylations represent a challenging problem because the mechanism of the reaction places the chiral environment distal to the bond breaking or making events responsible for the asymmetric induction. Furthermore, unlike virtually every other asymmetric process, many strategies can be employed for introduction of asymmetry and many different types of bonds can be formed. While over 100 different ligands have been designed, a family of ligands derived from 2-diphenylphosphinobenzoic or 1-naphthoic acid and chiral scalemic diamines have been successful in inducing excellent enantioselectivity by five different enantiodiscriminating events. These methods have already provided practical strategies towards numerous biological targets--some of which are adenosine and its enantiomer, aflatoxin B, aristeromycin, calanolide A and B, carbovir, cyclophellitol, ethambutol, galanthamine, mannostatin, neplanocin, phyllanthocin, sphingofungins E and F, tetraponaines, vigabatrin, and valienamine.
Trost
Barry M
BM
Department of Chemistry, Stanford University, CA 94305-5080, USA. bmtrost@stanford.edu
D000478:Alkylation; D000498:Allyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D002384:Catalysis; D008024:Ligands; D008956:Models, Chemical; D010165:Palladium / Q000737:chemistry*; D013237:Stereoisomerism; D013329:Structure-Activity Relationship
D000498:Allyl Compounds; D008024:Ligands; D010165:Palladium