3 years ago

Multidimensional Correlations in Asymmetric Catalysis through Parameterization of Uncatalyzed Transition States

Multidimensional Correlations in Asymmetric Catalysis through Parameterization of Uncatalyzed Transition States
Manuel Orlandi, F. Dean Toste, Matthew S. Sigman
The study of the oxidative amination of tetrahydroisoquinolines under chiral-anion phase-transfer (CAPT) catalysis by multidimensional correlation analysis (MCA) is revisited. The parameterization of the transition states (TSs) for the uncatalyzed reaction, the introduction of conformational descriptors, and the use of computed interaction energies and distances as parameters allowed access to a considerably simplified mathematical correlation of substrate and catalyst structure to enantioselectivity. The equation obtained is suggestive of key interactions occurring at the TS. Specifically, the CAPT catalyst is proposed to coordinate the intermediate iminium cation by P=O⋅⋅⋅H−O hydrogen-bonding and N⋅⋅⋅H−C electrostatic interactions. The conformational freedom of the benzyl substituent of the substrate was also found to be important in providing an efficient mode of molecular recognition. Worth another look: Multidimensional correlation analysis of a chiral-anion-catalyzed oxidative amination reaction was revisited. Parameterization of the transition states for the uncatalyzed reaction, the introduction of conformational descriptors, and the use of computed interaction energies and distances as parameters led to a simplified mathematical correlation of substrate and catalyst structure to enantioselectivity (NCI=noncovalent interaction).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201707644

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