Steps toward Rationalization of the Enantiomeric Excess of the Sakurai–Hosomi–Denmark Allylation Catalyzed by Biisoquinoline N,N’-Dioxides Using Computations

Catalysts

Coty Deluca¹  Roberto Peverati¹  Pierpaolo Morgante¹  Tegla E. Jones¹  Norito Takenaka¹  Gregory J. Aldrich¹ 

[1] Chemistry Program, Florida Institute of Technology, 150 W. University Blvd., Melbourne, FL 32901, USA;

关键词: DFT;    Lewis bases;    organocatalysis;    allyltrichlorosilane;   

DOI  :  10.3390/catal11121487

来源: DOAJ

【 摘 要 】

Allylation reactions of aldehydes are chemical transformations of fundamental interest, as they give direct access to chiral homoallylic alcohols. In this work, we focus on the full computational characterization of the catalytic activity of substituted biisoquinoline-N,N’-dioxides for the allylation of 2-naphthaldehyde. We characterized the structure of all transition states as well as identified the π stacking interactions that are responsible for their relative energies. Motivated by disagreement with the experimental results, we also performed an assessment of 34 different density functional methods, with the goal of assessing DFT as a general tool for understanding this chemistry. We found that the DFT results are generally consistent as long as functionals that correctly account for dispersion interactions are used. However, agreement with the experimental results is not always guaranteed. We suggest the need for a careful synergy between computations and experiments to correctly interpret the data and use them as a design tool for new and improved asymmetric catalysts.

【 授权许可】

Unknown