Tertiary amines are an important chemical motif due to their ubiquitous presence in many bioactive molecules.^[1] The ability to specifically cleave and re-form the C–N bonds in tertiary amines therefore holds high potential for chemical synthesis. Resulting from our on-going interest in catalytic C–X single bond metathesis reactions,^[2] we herein disclose the development of an iridium-catalyzed metathesis of tertiary alkyl amines.^[3] The synthetic utility and application of a metathesis approach of tertiary amines has been underexplored,^[4] as in the absence of any handles for selectivity such a process will typically result in complicated product mixtures due to a combinatorial explosion.

We have successfully developed strategies to tame this complexity and inter alia enable the selective cross-metathesis between selected tertiary amines. Beyond the evident applications in organic synthesis, we have further applied our system for molecular data storage harnessing the combinatorial complexity of statistically distributed product mixtures. Finally, we have also explored the possibility to utilize our amine metathesis methodology for the synthesis of new polyamine polymers.

Figure 1. Iridium-catalyzed metathesis reaction of tertiary alkyl amines and applications towards organic synthesis, molecular data storage and polymer chemistry.

[1] P. Ertl, E. Altmann, J. M. McKenna, Journal of Medicinal Chemistry, 2020, 63, 8408-8418.
[2] a) Z. Lian, B. N. Bhawal, P. Yu, B. Morandi, Science, 2017, 356, 1059-1063. b) T. Biberger, S. Makai, Z. Lian, B. Morandi, Angewandte Chemie International Edition, 2018, 57, 6940–6944.
[3] D. T. Egger et al., manuscript in preparation.
[4] Literature precedents for C–N bond metathesis: a) S. Murahashi, T. Hirano, T. Yano, Journal of the American Chemical Society, 1978, 100, 348-350. b) R. B. Wilson Jr., R. M. Laine, Journal of the American Chemical Society, 1985, 107, 361-369. c) Y. Shvo, M. Abed, Y. Blum, R. M. Laine, Israel Journal of Chemistry, 1986, 27, 267-275.