Origin of stereoselectivity in the amination of alcohols using cooperative asymmetric dual catalysis involving chiral counter-ions

• Published in: Chemical science (Cambridge) Vol. 9; no. 28; pp. 6126 - 6133
• Main Authors: Tribedi, Soumi, Hadad, Christopher M, Sunoj, Raghavan B
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 2018
• Subjects: Alcohol; Alcohols; Aniline; Asymmetry; Catalysis; Catalysts; Dehydrogenation; Density functional theory; Enantiomers; Hydrogen storage; Iridium; Phosphoric acid; Protonation; Stereoselectivity; Toluene
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c8sc01433g

Asymmetric catalysis using two chiral catalysts in combination using one-pot reaction conditions is in its initial stages of development and understanding. We employ density functional theory (SMD
/M06/6-31G**,SDD(Ir)) computations to shed light on the action of chiral phosphoric acid and a chiral Cp*Ir(diamine) in stereoinduction in an asymmetric amination reaction of an alcohol. First, the protonation of the Ir-diamine complex by the phosphoric acid forms an ion-pair of the active catalytic dyad. Both chiral catalysts are involved throughout the catalytic cycle, thus constituting an important example of true cooperative catalysis. A borrowing hydrogen mechanism operates, wherein the phosphate abstracts the hydroxyl proton of the alcohol while the electrophilic Ir(iii) simultaneously extracts the α-hydrogen to form a [Ir]-H species. The ketone thus derived from the alcohol through dehydrogenation condenses with aniline to form an imine. In the diastereocontrolling transition state, the hydride adds to the activated iminium, held in position in the chiral pocket of the catalytic dyad through a network of noncovalent interactions (C-H···π, N-H···O and C-H···O). The enantioselectivity in this DYKAT process is identified as taking place at an earlier stage of the catalytic cycle prior to the diastereo-determining transition state.