Spin Selectivity in Chiral Linked Systems

Spin Selectivity in Chiral Linked Systems This work has shown spin selectivity in electron transfer (ET) of diastereomers of (R,S)‐naproxen‐(S)‐N‐methylpyrrolidine and (R,S)‐naproxen‐(S)‐tryptophan dyads. Photoinduced ET in these dyads is interesting because of the still unexplained phenomenon of stereoselectivity in the drug activity of enantiomers. The chemically induced dynamic nuclear polarization (CIDNP) enhancement coefficients of (R,S)‐diastereomers are double those of the (S,S)‐analogue. These facts are also interesting because spin effects are among the most sensitive, even to small changes in spin and molecular dynamics of paramagnetic particles. Therefore, CIDNP reflects the difference in magnetoresonance parameters (hyperfine interaction constants (HFIs), g‐factor difference) and lifetimes of the paramagnetic forms of (R,S)‐ and (S,S)‐diastereomers. The difference in HFI values for diastereomers has been confirmed by a comparison of CIDNP experimental enhancement coefficients with those calculated. Additionally, the dependence of the CIDNP enhancement coefficients on diastereomer concentration has been observed for the naproxen‐N‐methylpyrrolidine dyad. This has been explained by the participation of ET in homo‐(R,S‐R,S or S,S‐S,S) and hetero‐(R,S‐S,S) dimers of dyads. In this case, the effectivity of ET, and consequently, CIDNP, is supposed to be different for (R,S)‐ and (S,S)‐homodimers, heterodimers, and monomers. The possibility of dyad dimer formation has been demonstrated by using high‐resolution X‐ray and NMR spectroscopy techniques. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Chemistry - A European Journal Wiley

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Publisher
Wiley Subscription Services, Inc., A Wiley Company
Copyright
© 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
ISSN
0947-6539
eISSN
1521-3765
D.O.I.
10.1002/chem.201705863
Publisher site
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Abstract

This work has shown spin selectivity in electron transfer (ET) of diastereomers of (R,S)‐naproxen‐(S)‐N‐methylpyrrolidine and (R,S)‐naproxen‐(S)‐tryptophan dyads. Photoinduced ET in these dyads is interesting because of the still unexplained phenomenon of stereoselectivity in the drug activity of enantiomers. The chemically induced dynamic nuclear polarization (CIDNP) enhancement coefficients of (R,S)‐diastereomers are double those of the (S,S)‐analogue. These facts are also interesting because spin effects are among the most sensitive, even to small changes in spin and molecular dynamics of paramagnetic particles. Therefore, CIDNP reflects the difference in magnetoresonance parameters (hyperfine interaction constants (HFIs), g‐factor difference) and lifetimes of the paramagnetic forms of (R,S)‐ and (S,S)‐diastereomers. The difference in HFI values for diastereomers has been confirmed by a comparison of CIDNP experimental enhancement coefficients with those calculated. Additionally, the dependence of the CIDNP enhancement coefficients on diastereomer concentration has been observed for the naproxen‐N‐methylpyrrolidine dyad. This has been explained by the participation of ET in homo‐(R,S‐R,S or S,S‐S,S) and hetero‐(R,S‐S,S) dimers of dyads. In this case, the effectivity of ET, and consequently, CIDNP, is supposed to be different for (R,S)‐ and (S,S)‐homodimers, heterodimers, and monomers. The possibility of dyad dimer formation has been demonstrated by using high‐resolution X‐ray and NMR spectroscopy techniques.

Journal

Chemistry - A European JournalWiley

Published: Jan 12, 2018

Keywords: ; ; ; ;

References

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