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Stellios Arseniyadis

DNA-based asymmetric catalysis: Perhaps a new way to approach asymmetric C−H activation

Stellios Arseniyadis

DNA-based artificial metalloenzymes have recently drawn considerable attention because of their unique features that comprise a chemically stable chiral double helix associated with many programmable secondary structures. Since the pioneering work of Roelfes and Feringa,1 the field of DNA-based asymmetric catalysis has been thriving in the last few years, resulting in the development of a handful of highly selective synthetic transformations by several groups2 including ours.3 The concept of DNA-based asymmetric catalysis lies in embedding an achiral transition metal catalyst in a DNA double helix that provides the necessary chiral microenvironment to promote the formation of one enantiomer over another for any given reaction. The most recent efforts to unveil new reactivities have been accompanied with the willingness to understand the mechanisms by which the chirality is transferred. We’ll present here some of our most recent results with the aim to trigger some thinking on how to extend the method to asymmetric C−H functionalization processes.

References:
1. Roelfes, G.; Feringa, B. L. Angew. Chem., Int. Ed. 2005, 44, 3230.
2. (a) Duchemin, N.; Heath-Apostolopoulos, I.; Smietana, M.; Arseniyadis, S. Org. Biomol. Chem. 2017, 15, 7072.
(b) Drienovska, I.; Roelfes, G. Isr. J. Chem. 2015, 55, 21. (c) Park, S.; Sugiyama, H. Molecules 2012, 17, 12792.
(d) Boersma A. J.; Megens, R. P.; Feringa, B. L.; Roelfes, G. Chem. Soc. Rev. 2010, 39, 2083.
3. (a) Mansot, J.; Aubert, S.; Duchemin, N.; Vasseur, J.-J.; Arseniyadis, S.; Smietana, M. Chem. Sci. 2019, 2875.
(b) Duchemin, N.; Skiredj, A.; Mansot, J.; Leblanc, K.; Vasseur, J.-J.; Beniddir, M. A.; Evanno, L.; Poupon, E.; Smietana,
M.; Arseniyadis, S. Angew. Chem., Int. Ed. 2018, 57, 11786. (c) Duchemin, N.; Benedetti, E.; Bethge, L.; Vonhoff, S.;
Klussmann, S.; Vasseur, J.-J.; Cossy, J.; Smietana, M.; Arseniyadis, S. Chem. Commun. 2016, 52, 8604. (d) Amirbekyan,
K.; Duchemin, N.; Benedetti, E.; Joseph, R.; Colon, A.; Markarian, S. A.; Bethge, L.; Vonhoff, S.; Klussmann, S.; Cossy, J.;
Vasseur, J.-J.; Arseniyadis, S.; Smietana, M. ACS Catal. 2016, 6, 3096. (e) Benedetti, E.; Duchemin, N.; Bethge, L.;
Vonhoff, S.; Klussmann, S.; Vasseur, J.-J.; Cossy, J.; Smietana, M.; Arseniyadis, S. Chem. Commun. 2015, 51, 6076.
(f) Wang, J.; Benedetti, E.; Bethge, L.; Vonhoff, S.; Klussmann, S.; Vasseur, J.-J.; Cossy, J.; Smietana, M.; Arseniyadis, S.
Angew. Chem. Int. Ed. 2013, 52, 11546.

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