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Structure–Activity Relationship in the Iridium‐Catalyzed Isomerization of Primary Allylic Alcohols
Author(s) -
Mantilli Luca,
Gérard David,
Besnard Céline,
Mazet Clément
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201200369
Subject(s) - isomerization , chemistry , allylic rearrangement , iridium , catalysis , cationic polymerization , pyridine , nucleophile , medicinal chemistry , cyclooctadiene , primary (astronomy) , organic chemistry , photochemistry , computational chemistry , physics , astronomy
The evaluation of a series of cationic iridium complexes in the isomerization of primary allylic alcohols has revealed the unique ability of Crabtree catalysts [(Cy 3 P)(C 6 H 5 N)Ir(cod)] · X 1a (X = PF 6 ) and 1b (X = BAr F ; cod = 1,5‐cyclooctadiene) to catalyze efficiently this transformation. Emphasis has been placed on understanding the electronic factors that govern the catalytic process by using a range of para ‐substituted pyridine N‐donor ligands. Excellent correlations between analytical data ( 13 C NMR chemical shift; ν CO ) and established thermodynamic and kinetic parameters (p K a , Mayr nucleophilicity parameter N ) have been elaborated. Overall, the results obtained point to the possibility of qualitatively predicting the activity of Crabtree catalyst analogues in the isomerization of primary allylic alcohols.