Ligand-dependent catalytic cycle and role of styrene in nickel-catalyzed anhydride cross-coupling: evidence for turnover-limiting reductive elimination.
Results from a mechanistic study on the Ni(COD)2-bipy-catalyzed alkylation of anhydrides are consistent with turnover-limiting reductive elimination at high Et2Zn concentrations. While the presence of styrene does not affect the initial rate of alkylation, it appears to inhibit catalyst decomposition and provides higher product yield at long reaction times. In contrast, Ni(COD)2-iPrPHOX-catalyzed anhydride alkylation proceeds through two competing catalytic cycles differentiated by the presence of styrene. The presence of styrene in this system appears to accelerate rate-limiting oxidative addition and promotes the cycle which proceeds 4 times more rapidly and with much higher enantioselectivity than its styrene-lacking counterpart.
Johnson
Jeffrey B
JB
Colorado State University, Fort Collins, CO 80523, USA.
Bercot
Eric A
EA
Rowley
John M
JM
Coates
Geoffrey W
GW
Rovis
Tomislav
T
D015082:2,2'-Dipyridyl / Q000737:chemistry*; D019840:2-Propanol / Q000737:chemistry; D000478:Alkylation; D000812:Anhydrides / Q000737:chemistry*; D002384:Catalysis; D007700:Kinetics; D008024:Ligands; D008956:Models, Chemical; D009532:Nickel / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010081:Oxazolone / Q000737:chemistry; D010084:Oxidation-Reduction; D017976:Phosphorus Acids / Q000737:chemistry; D020058:Styrene / Q000737:chemistry*; D013696:Temperature; D015032:Zinc / Q000737:chemistry
D000812:Anhydrides; D008024:Ligands; D009942:Organometallic Compounds; D017976:Phosphorus Acids; D010081:Oxazolone; D020058:Styrene; D015082:2,2'-Dipyridyl; D009532:Nickel; D015032:Zinc; D019840:2-Propanol