Experimental and theoretical analysis of asymmetric induction in heterogeneous catalysis: diastereoselective hydrogenation of chiral alpha-hydroxyketones over Pt catalyst.
Assessing the origin of asymmetric induction in heterogeneously catalyzed hydrogenation is a challenging task. In this work, hydrogenation of a chiral compound, (R)-1-hydroxy-1-phenyl-2-propanone [(R)-PAC], in toluene over cinchonidine modified and unmodified Pt/Al(2)O(3) was studied. To reveal the detailed reaction mechanism and the origin of stereoselectivity in the Pt-catalyzed hydrogenation of the CO double bond, the structures and energies of several adsorption modes of (R)-PAC as well as whole reaction paths for hydrogenation were investigated on Pt(111) by density functional theory (DFT). In agreement with experimental results, the theoretically obtained potential energy profiles for the studied hydrogenation mechanisms implied that (1R,2S)-1-phenyl-1,2-propanediol is formed in excess with respect to the other diastereomeric product diol, (1R,2R)-1-phenyl-1,2-propanediol. Generally, if the elementary hydrogen addition step was thermodynamically more favorable on one of the two diastereotopic faces, it was also kinetically preferred on the same face, and vice versa. Pairwise addition of hydrogen was the most energetically favorable mechanism. Adsorption and hydrogenation of other structurally similar chiral alpha-hydroxyketones, (R)-3-hydroxy-2-butanone and (R)-2-hydroxy-1-cyclohexanone, were also studied computationally on Pt(111). The results showed that cluster model DFT calculations can be used to assess (dia)stereoselectivity in metal-catalyzed hydrogenation of even such complex organic molecules as studied here.
Busygin
Igor
I
Laboratory of Organic Chemistry, Abo Akademi University, FI-20500 Turku/Abo, Finland.
Taskinen
Antti
A
Nieminen
Ville
V
Toukoniitty
Esa
E
Stillger
Thomas
T
Leino
Reko
R
Murzin
Dmitry Yu
DY
D000327:Adsorption; D002384:Catalysis; D047188:Chalcones / Q000737:chemistry; D002625:Chemistry, Organic / Q000379:methods*; D006859:Hydrogen / Q000737:chemistry; D006865:Hydrogenation; D007659:Ketones / Q000737:chemistry*; D007700:Kinetics; D008968:Molecular Conformation; D010984:Platinum / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
D047188:Chalcones; D007659:Ketones; D010984:Platinum; D006859:Hydrogen; C100349:1-phenyl-1,2-propanedione