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Dual wavelength asymmetric photochemical synthesis with circularly polarized light

Dual wavelength asymmetric photochemical synthesis with circularly polarized light
Dual wavelength asymmetric photochemical synthesis with circularly polarized light
Asymmetric photochemical synthesis using circularly polarized (CP) 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 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.
1478-6524
3853-3862
Richardson, Robert D.
5d4a9393-524b-4b88-a2b2-2bf3b6e7c3e6
Baud, Matthias
8752d519-3d33-43b6-9a77-ab731d410c2e
Weston, Claire E.
105a0338-fc15-4ed4-84a2-b5a8d6f63d31
Rzepa, Henry S.
1c998700-a3e1-48ec-9e7d-e502b721f55d
Kuimova, Marina K.
3e327167-cd55-4b4b-a209-a861367f543e
Fuchter, Matthew J.
a98083c4-2a98-4844-8289-5468ec472801
Richardson, Robert D.
5d4a9393-524b-4b88-a2b2-2bf3b6e7c3e6
Baud, Matthias
8752d519-3d33-43b6-9a77-ab731d410c2e
Weston, Claire E.
105a0338-fc15-4ed4-84a2-b5a8d6f63d31
Rzepa, Henry S.
1c998700-a3e1-48ec-9e7d-e502b721f55d
Kuimova, Marina K.
3e327167-cd55-4b4b-a209-a861367f543e
Fuchter, Matthew J.
a98083c4-2a98-4844-8289-5468ec472801

Richardson, Robert D., Baud, Matthias, Weston, Claire E., Rzepa, Henry S., Kuimova, Marina K. and Fuchter, Matthew J. (2015) Dual wavelength asymmetric photochemical synthesis with circularly polarized light. Chemical Science, 6 (7), 3853-3862. (doi:10.1039/C4SC03897E).

Record type: Article

Abstract

Asymmetric photochemical synthesis using circularly polarized (CP) 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 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.

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Accepted/In Press date: 16 April 2015
Published date: 16 April 2015

Identifiers

Local EPrints ID: 400500
URI: http://eprints.soton.ac.uk/id/eprint/400500
ISSN: 1478-6524
PURE UUID: 48559992-9f83-42d7-b679-16ca588bd04d
ORCID for Matthias Baud: ORCID iD orcid.org/0000-0003-3714-4350

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Date deposited: 16 Sep 2016 15:16
Last modified: 13 Nov 2021 02:54

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Contributors

Author: Robert D. Richardson
Author: Matthias Baud ORCID iD
Author: Claire E. Weston
Author: Henry S. Rzepa
Author: Marina K. Kuimova
Author: Matthew J. Fuchter

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