Preparation of a Highly Congested Carbazoyl-Derived P,N-Type Phosphine Ligand for Acetone Monoarylations
State Key Laboratory of Chirosciences
and Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, People’s Republic of China
and Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, People’s Republic of China
Organometallics, Article ASAP
DOI: 10.1021/acs.organomet.6b00154
Publication Date (Web): March 31, 2016
Copyright © 2016 American Chemical Society
*E-mail for F.Y.K.: fuk-yee.kwong@polyu.edu.hk.
Abstract
We report a newly developed carbazoyl-derived P,N-type phosphine ligand (L1) for the monoarylation of acetone with aryl chlorides. The proposed Pd(dba)2/L1
catalyst exhibited remarkable catalytic reactivity toward highly
electron rich and sterically congested aryl chlorides, with catalyst
loading as low as 0.1 mol % of Pd along with excellent chemoselectivity.
A reaction rate study of the system using electronically diverse aryl
chlorides determined the mechanisms regarding the rate-limiting steps in
this reaction. The oxidative addition adduct of Pd-PhenCar-Phos with p-chlorotoluene showed the participation of N–Pd coordination in the metal complex. The isolated palladium complex C1
could be utilized as a precatalyst in the transformation and achieved
performance comparable to that of the in situ generated palladium
species.
catalyst exhibited remarkable catalytic reactivity toward highly
electron rich and sterically congested aryl chlorides, with catalyst
loading as low as 0.1 mol % of Pd along with excellent chemoselectivity.
A reaction rate study of the system using electronically diverse aryl
chlorides determined the mechanisms regarding the rate-limiting steps in
this reaction. The oxidative addition adduct of Pd-PhenCar-Phos with p-chlorotoluene showed the participation of N–Pd coordination in the metal complex. The isolated palladium complex C1
could be utilized as a precatalyst in the transformation and achieved
performance comparable to that of the in situ generated palladium
species.
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