The Electron Spin as a Chiral Reagent.
chiral-induced spin selectivity
chirality
electrochemistry
enantioselectivity
spin
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
20 Jan 2020
20 Jan 2020
Historique:
received:
06
09
2019
revised:
16
10
2019
pubmed:
18
10
2019
medline:
18
10
2019
entrez:
18
10
2019
Statut:
ppublish
Résumé
We show that enantioselective reactions can be induced by the electron spin itself and that it is possible to replace a conventional enantiopure chemical reagent by spin-polarized electrons that provide the chiral bias for enantioselective reactions. Three examples of enantioselective chemistry resulting from electron-spin polarization are presented. One demonstrates the enantioselective association of a chiral molecule with an achiral self-assembled monolayer film that is spin-polarized, while the other two show that the chiral bias provided by the electron helicity can drive both reduction and oxidation in enantiospecific electrochemical reactions. In each case, the enantioselectivity does not result from enantiospecific interactions of the molecule with the ferromagnetic electrode but from the polarized spin that crosses the interface between the substrate and the molecule. Furthermore, the direction of the electron-spin polarization defines the handedness of the enantioselectivity. This work demonstrates a new mechanism for realizing enantioselective chemistry.
Identifiants
pubmed: 31621990
doi: 10.1002/anie.201911400
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
1653-1658Subventions
Organisme : John Templeton Foundation
ID : 60796
Organisme : Volkswagen Foundation
ID : 88 367
Informations de copyright
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Références
L. D. Barron, Science 1994, 266, 1491-1492.
G. L. J. A. Rikken, E. Raupach, Nature 1997, 390, 493-494.
G. L. J. A. Rikken, E. Raupach, Nature 2000, 405, 932-935.
C. Wattanakit, Curr. Opin. Electrochem. 2018, 7, 54-60.
B. F. Watkins, J. R. Behling, E. Kariv, L. L. Miller, J. Am. Chem. Soc. 1975, 97, 3549-3550.
H. Maekawa, K. Itoh, S. Goda, I. Nishiguchi, Chirality 2003, 15, 95-100.
L. Dong, et al., Anal. Chem. 2017, 89, 9695-9702.
I. Mogi, R. Morimoto, R. Aogaki, K. Watanabe, Sci. Rep. 2013, 3, 2574.
M. Gazzotti, et al., Elect. Acta 2018, 286, 271-278.
D. E. Koshland, Angew. Chem. Int. Ed. Engl. 1995, 33, 2375-2378;
Angew. Chem. 1994, 106, 2468-2472.
K. Banerjee-Ghosh, et al., Science 2018, 360, 1331-1334.
A. Kumar, et al., Proc. Natl. Acad. Sci. USA 2017, 114, 2474-2478.
E. Andris, et al., Angew. Chem. Int. Ed. 2017, 56, 14057-14060;
Angew. Chem. 2017, 129, 14245-14248.
J. Wang, C. Doubleday, Jr., N. J. Turro, J. Am. Chem. Soc. 1989, 111, 3962-3965.
R. Naaman, D. H. Waldeck, Annu. Rev. Phys. Chem. 2015, 66, 263-281.
K. Michaeli, N. Kantor-Uriel, R. Naaman, D. H. Waldeck, Chem. Soc. Rev. 2016, 45, 6478-6487.
R. Naaman, Y. Paltiel, D. H. Waldeck, Nat. Rev. Chem. 2019, 3, 250-260.
B. V. Göhler, et al., Science 2011, 331, 894-897.
R. A. Rosenberg, D. Mishra, R. Naaman, Angew. Chem. Int. Ed. 2015, 54, 7295-7298;
Angew. Chem. 2015, 127, 7403-7406.
J. C. Bachman, et al., Nat. Commun. 2015, 6, 7040.
R. J. Waltman, J. Bargon, Can. J. Chem. 1986, 64, 76-95.
I. Mogi, K. Watanabe, J. Solid State Electrochem. 2007, 11, 751-756.
A. Alija, et al., Phys. Rev. B 2010, 82, 184529.