Linear Free-Energy Relationships in the Rational Development of New Chiral Catalysts Based on Primary Amine Catalysis.

Understanding how electronic effects influence the activity and selectivity of organocatalysts remains a challenge for the rational development of more efficient catalytic systems.¹ This work aims to develop chiral aminocatalysts as an alternative to tert-butylglycine derived catalysts and investigate the influence of electronic effects through linear free energy relationships (LFERs).² A series of aminocatalysts bearing aliphatic primary amines, β-tertiary amines, and electronically tunable diarylsilyloxymethyl groups was synthesized,³˒⁴ inspired by privileged scaffolds for aminocatalysis.¹˒⁵ The synthesized catalysts will be evaluated in model reactions to correlate Hammett constants with catalytic parameters, including turnover number (TON), turnover frequency (TOF), reactivity, and stereoselectivity.² These studies are expected to provide valuable insights into the rational design of more active and selective organocatalysts.