Brønsted base-modulated regioselectivity in the aerobic oxidative amination of styrene catalyzed by palladium.
Palladium(II)-catalyzed aerobic oxidative amination of styrene with oxazolidinone proceeds with catalyst-controlled regioselectivity: (CH3CN)2PdCl2 (1) and (Et3N)2PdCl2 (2) catalyze formation of the anti-Markovnikov and Markovnikov enecarbamate products, 3 and 4, respectively. Kinetic studies and deuterium kinetic isotope effects demonstrate that these two reactions possess different rate-limiting steps, and the data indicate that the product regiochemistry arises from the presence or absence of an effective Brønsted base in the reaction. In the presence of a Brønsted base such as triethylamine or acetate, the kinetically preferred Markovnikov aminopalladation adduct of styrene is trapped via rapid deprotonation of a zwitterionic intermediate and leads to formation of 4. In the absence of an effective Brønsted base, however, slow deprotonation of this adduct enables aminopalladation to be reversible, and product formation proceeds through the thermodynamically preferred anti-Markovnikov aminopalladation adduct to yield 3.
Timokhin
Vitaliy I
VI
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.
Stahl
Shannon S
SS
D000332:Aerobiosis; D000586:Amination; D000588:Amines / Q000138:chemical synthesis*; D002384:Catalysis; D007700:Kinetics; D023303:Oxazolidinones / Q000737:chemistry*; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry; D020058:Styrene / Q000737:chemistry*; D013379:Substrate Specificity; D013816:Thermodynamics
D000588:Amines; D023303:Oxazolidinones; D020058:Styrene; D010165:Palladium