Premium
A New Platform for Designing Ligands for Asymmetric Induction in Allylic Alkylations
Author(s) -
Trost Barry M.,
Breit Bernhard,
Peukert Stefan,
Zambrano Jorge,
Ziller Joseph W.
Publication year - 1995
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199523861
Subject(s) - ligand (biochemistry) , chemistry , nucleophile , amide , linker , catalysis , stereochemistry , asymmetric induction , allylic rearrangement , coordination sphere , substrate (aquarium) , enantiomer , tsuji–trost reaction , metal , crystallography , nucleophilic addition , combinatorial chemistry , enantioselective synthesis , crystal structure , organic chemistry , receptor , biochemistry , oceanography , geology , computer science , operating system
Simply inverting the orientation of the amide function as in 1 compared to that of the ligand series derived from 2‐diphenylphosphinobenzoic acid affects the enantiomeric discriminating step in the Pd‐catalyzed nucleophilic alkylation of meso ‐1,4‐dihydroxy‐2‐cycloalkenes. In reactions such as this, the bond‐making or ‐breaking event occurs outside the coordination sphere of the metal. The chiral scaffold of the ligand is connected to the metal atom by a linker (here 2‐diphenylphosphinoaniline), and the preferred conformation of the catalysts provides “chiral spaces” for the substrate–a conclusion supported by X‐ray crystallography.