Michal Schnürch

The observation and investigation of nonlinear effects [1,2] in catalytic reactions provides valuable mechanistic insight. However, the applicability of this method was, until now, limited to molecules possessing chirality and therefore to asymmetric synthesis. Within this contribution, the concept of nonlinear effects is expanded to catalytic reactions beyond asymmetric catalysis by using derivatives instead of enantiomers and by considering rates instead of enantiomeric excess [3]. To demonstrate our concept, the direct alkylation of indoles with alkyl bromides recently published by the group of Bach [4] was used as an example. In this completely achiral reaction, a clear nonlinear effect was observed, which shows that by exceeding the limitation to asymmetric reactions, the study of nonlinear effects can become a general tool to elucidate reaction mechanisms.

References:
[1] Puchot, C. Samuel, O. Dunach, E. Zhao, S. Agami, C. Kagan, H. J. Am. Chem. Soc. 1986, 108, 2353.
[2] Blackmond, D. G. Acc. Chem. Res. 2000, 33, 402.
[3] Pollice, R. Schnürch, M. Chem. Eur. J. 2016, 22, 5637.
[4] L. Jiao, E. Herdtweck, T. Bach, J. Am. Chem. Soc. 2012, 134, 14563.