%0 Journal Article %A Paras, Nick A. %A W. C. MacMillan, David %D 2002 %T The Enantioselective Organocatalytic 1,4-Addition of Electron-Rich Benzenes to α,β-Unsaturated Aldehydes %U https://acs.figshare.com/articles/journal_contribution/The_Enantioselective_Organocatalytic_1_4-Addition_of_Electron-Rich_Benzenes_to_-Unsaturated_Aldehydes/3642954 %R 10.1021/ja025981p.s001 %2 https://acs.figshare.com/ndownloader/files/5731758 %K enantioselective organocatalytic alkylation %K benzylic stereogenicity %K chiral synthon %K aldehyde substrates %K butylimidazolidinone amine catalyst %K iminium catalysis %K catalyst quantities %K mol %K conjugate addition %K agent synthesis %K catalyst loadings %K unsubstituted anilines %K organocatalytic transformation %K enantioselective construction %X The first enantioselective organocatalytic alkylation of electron-rich benzene rings with α,β-unsaturated aldehydes has been accomplished. The use of iminium catalysis has provided a new strategy for the enantioselective construction of benzylic stereogenicity, an important chiral synthon for natural product and medicinal agent synthesis. The (2S,5S)-5-benzyl-2-tert-butylimidazolidinone amine catalyst has been found to mediate the conjugate addition of a wide variety of substituted and unsubstituted anilines to unsaturated aldehydes. A diverse spectrum of aldehyde substrates can also be accommodated in this new organocatalytic transformation. While catalyst quantities of 10 mol % were generally employed in this study, successful alkylations conducted with catalyst loadings as low as 1 mol % are described. %I ACS Publications