Computed conformations of cis-dinaphthylethene 1

Title: Computed conformations of cis-dinaphthylethene 1
Author(s): Rzepa, HS
E.Weston, C
K. Kuimova, M
D. Richardson, R
G. J. Baud, M
J. Fuchter, M
Item Type: Dataset
Abstract: Asymmetric photochemical synthesis using circularly polarized light is theoretically attractive as a means of absolute asymmetric synthesis and postulated as an explanation for homochirality on Earth. Using an asymmetric photochemical synthesis of a dihydrohelicene as an example, we demonstrate the principle that two wavelengths of circularly polarized (CP) light can be used to control separate reactions. In doing so, a photostationary state (PSS) is set up in such a way that the enantiomeric induction intrinsic to each step can combine additively, significantly increasing the asymmetric induction possible in these reactions. Moreover, we show that the effects of this dual wavelength approach can be accurately determined by kinetic modelling of the PSS. Finally, by coupling a PSS to a thermal reaction to trap the photoproduct, we demonstrate that higher enantioselectivity can be achieved than that obtainable with single wavelength irradiation, without compromising the yield of the final product.
Asymmetric photochemical synthesis using circularly polarized light is theoretically attractive as a means of absolute asymmetric synthesis and postulated as an explanation for homochirality on Earth. Using an asymmetric photochemical synthesis of a dihydrohelicene as an example, we demonstrate the principle that two wavelengths of circularly polarized (CP) light can be used to control separate reactions. In doing so, a photostationary state (PSS) is set up in such a way that the enantiomeric induction intrinsic to each step can combine additively, significantly increasing the asymmetric induction possible in these reactions. Moreover, we show that the effects of this dual wavelength approach can be accurately determined by kinetic modelling of the PSS. Finally, by coupling a PSS to a thermal reaction to trap the photoproduct, we demonstrate that higher enantioselectivity can be achieved than that obtainable with single wavelength irradiation, without compromising the yield of the final product.
Asymmetric photochemical synthesis using circularly polarized light is theoretically attractive as a means of absolute asymmetric synthesis and postulated as an explanation for homochirality on Earth. Using an asymmetric photochemical synthesis of a dihydrohelicene as an example, we demonstrate the principle that two wavelengths of circularly polarized (CP) light can be used to control separate reactions. In doing so, a photostationary state (PSS) is set up in such a way that the enantiomeric induction intrinsic to each step can combine additively, significantly increasing the asymmetric induction possible in these reactions. Moreover, we show that the effects of this dual wavelength approach can be accurately determined by kinetic modelling of the PSS. Finally, by coupling a PSS to a thermal reaction to trap the photoproduct, we demonstrate that higher enantioselectivity can be achieved than that obtainable with single wavelength irradiation, without compromising the yield of the final product.
Publication Date: 27-Feb-2015
URI: http://hdl.handle.net/10044/1/30147
DOI: https://dx.doi.org/10.6084/m9.figshare.1317341.v1
Keywords: photochemical
synthesis
Computational Chemistry
Organic Chemistry
Stereochemistry
photochemical
synthesis
Computational Chemistry
Organic Chemistry
Stereochemistry
Appears in Collections:Faculty of Natural Sciences - Research Data



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