Computational determination of the Tsuji asymmetrical allylation reaction mechanism

INOR 904

John A Keith, johnk@wag.caltech.edu1, Jonas Oxgaard, oxgaard@wag.caltech.edu1, Brian M. Stoltz, stoltz@caltech.edu2, and William A. Goddard III, wag@wag.caltech.edu3. (1) Materials and Process Simulation Center, California Institute of Technology, Beckman Institute (139-73), Pasadena, CA 91125, (2) Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd., MC 164-30, Pasadena, CA 91125, (3) Materials and Process Simulation Center, California Insitute of Technology, California Insitute of Technology, 139-74, Pasadena, CA 91125
A proposed mechanism rationalizing the unique performance of the Tsuji-asymmetrical allylation reaction for prochiral nucleophiles and non-prochiral allyl groups was determined with density functional theory. Calculations suggest a distinct preference for an internal nucleophilic attack followed by interconversion from a 5-coodinate Pd complex to a 4-coordinate complex compared to non-enantioselective external nucleophilic attack. Non-rate determining reductive elimination proceeds in a non-traditional manner generating the formation of the product and a Pd0 complex.

 

Computational Chemistry
8:30 AM-12:10 PM, Wednesday, 13 September 2006 Moscone Center -- Room 305, Oral

Division of Inorganic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006