Nickel(II)-catalyzed highly enantioselective hydrophosphination of methacrylonitrile
Aaron D Sadow1, Isabelle Haller, Luca Fadini
1Department of Chemistry and Applied Biosciences, Swiss Federal Institute of Technology, ETH Hönggerberg, CH-8093 Zürich, Switzerland.
Abstract:
The dicationic Ni(II) complex [Ni(Pigiphos)(THF)](ClO4)2, [1](ClO4)2 ((R)-(S)-Pigiphos = bis-{(R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyl}cyclohexylphosphine), catalyzes the addition of bulky aliphatic secondary phosphines to methaacrylonitrile. This hydrophosphination reaction reaches TON = 900 and enantioselectivities up to 94%. A catalytic cycle involving 1,4-conjugate addition of R2PH to methacrylonitrile is supported by the isolation and characterization of a catalytically active N-coordinated, methacrylonitrile Ni complex.
Related Concept Videos
Acid-Catalyzed Hydration of Alkenes
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
Acid-Catalyzed Dehydration of Alcohols to Alkenes
Acid Halides to Esters: Alcoholysis
Esters to Carboxylic Acids: Acid-Catalyzed Hydrolysis
During hydrolysis, the ester is first activated towards nucleophilic attack through the protonation of the carboxyl oxygen atom by the acid catalyst. The protonation makes the ester carbonyl carbon more electrophilic. In the next step, water acts as a nucleophile and adds to the...
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation


