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Pyrrolidinopyridines in Palladium‐Catalyzed Allylic Substitutions − Conformation of the Ligand
Author(s) -
Stranne Robert,
Moberg Christina
Publication year - 2001
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200106)2001:11<2191::aid-ejoc2191>3.0.co;2-x
Subject(s) - chemistry , substituent , palladium , absolute configuration , allylic rearrangement , pyridine , stereochemistry , malonate , ligand (biochemistry) , ring (chemistry) , tsuji–trost reaction , medicinal chemistry , catalysis , organic chemistry , biochemistry , receptor
The ( R , R )‐2‐[(2,5‐dimethylpyrrolidin‐1‐yl)methyl]pyridines 4 , 5 , and 6 carrying a 2‐hydroxyalkyl, 2‐alkoxyalkyl or 2‐siloxyalkyl substituent in the 6‐position of the pyridine ring were prepared and assessed in palladium‐catalyzed allylations of 1,3‐diphenylpropenyl acetate with malonate. All ligands having 6‐substituents with an S absolute configuration afforded the product with an R configuration in 80−84% ee , whereas those having substituents with an R absolute configuration gave the opposite product with a selectivity depending on the nature of the substituent (8−74% ee ). It is believed that the enantioselectivity is dependent on the conformation of that substituent.