Experimental and Computational Gas Phase Acidities of Conjugate Acids of Triazolylidene Carbenes: Rationalizing Subtle Electronic Effects

Yijie Niu, Ning Wang, Alberto Muñoz, Jiahui Xu, Hao Zeng, Tomislav Rovis, Jeehiun K. Lee

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

In recent years, triazolylidene carbenes have come to the forefront as important organocatalysts for a wide range of reactions. The fundamental properties of these species, however, remain largely unknown. Herein, the gas phase acidities have been measured and calculated for a series of triazolium cations (the conjugate acids of the triazolylidene carbenes) that have not been heretofore examined in vacuo. The results are discussed in the context of these species as catalysts. We find correlations between the gas phase acidity and selectivity in two Umpolung reactions catalyzed by these species; such correlations are the first of their kind. We are able to use these linear correlations to improve reaction enantioselectivity. These results establish the possibility of using these thermochemical properties to predict reactivity in related transformations.

Original languageEnglish (US)
Pages (from-to)14917-14930
Number of pages14
JournalJournal of the American Chemical Society
Volume139
Issue number42
DOIs
StatePublished - Oct 25 2017

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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