Regio- and Stereoselectivity of the Norrish–Yang Photocyclization of Dialkyl 1,2-Diketones: Solution versus Solid State Photochemistry of Two Polymorphs
As shown by X-ray crystallography, crystals of 3β-acetoxy-16,17-seco-17,20-dioxopregn-5-ene-16-nitrile are dimorphic. The regioselectivity of the Norrish–Yang type II photocyclization under visible light of this steroidal 1,2-diketone, which bears primary, secondary, and tertiary nonequivalent abstractable γ-hydrogens, dramatically increases in the crystalline state of both polymorphs. X-ray crystallography and molecular mechanics calculations reveal crystal structure–solid state photochemistry relationships.
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2022-10-25
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Subjects: | Crystal structure, crystals, diffraction, irradiation, photocyclization, |
Online Access: | http://hdl.handle.net/10261/288760 |
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dig-ipna-es-10261-2887602023-02-09T11:54:32Z Regio- and Stereoselectivity of the Norrish–Yang Photocyclization of Dialkyl 1,2-Diketones: Solution versus Solid State Photochemistry of Two Polymorphs Álvarez-Dorta, Dimitri León, Elisa I. Martín, Ángeles Kennedy, Alan R. Pérez-Martín, Inés Shankland, Kenneth Suárez, Ernesto Ministerio de Economía y Competitividad (España) CSIC - Unidad de Recursos de Información Científica para la Investigación (URICI) Crystal structure crystals diffraction irradiation photocyclization As shown by X-ray crystallography, crystals of 3β-acetoxy-16,17-seco-17,20-dioxopregn-5-ene-16-nitrile are dimorphic. The regioselectivity of the Norrish–Yang type II photocyclization under visible light of this steroidal 1,2-diketone, which bears primary, secondary, and tertiary nonequivalent abstractable γ-hydrogens, dramatically increases in the crystalline state of both polymorphs. X-ray crystallography and molecular mechanics calculations reveal crystal structure–solid state photochemistry relationships. Financial support by the Investigation Programs of the Ministerio de Economía y Competitividad (CTQ2010-18244) is acknowledged. D.A.-D. thanks the Ministerio de Economía y Competitividad for a fellowship. The authors acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI). Peer reviewed 2023-02-09T11:54:32Z 2023-02-09T11:54:32Z 2022-10-25 artículo Journal of Organic Chemistry, 87(21), 14940–14947, 1-8 (2022) 0022-3263 http://hdl.handle.net/10261/288760 10.1021/acs.joc.2c01855 1520-6904 en #PLACEHOLDER_PARENT_METADATA_VALUE# info:eu-repo/grantAgreement/MICINN//CTQ2010-18244/ES/APLICACIONES SINTETICAS DE LOS PROCESOS DE TRANSFERENCIA INTRAMOLECULAR DE HIDROGENO EN SISTEMAS DE CARBOHIDRATOS. OBTENCION DE NUEVOS SINTONES QUIRALES/ Publisher's version https://doi.org/10.1021/acs.joc.2c01855 Sí open ACS Publications |
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Crystal structure crystals diffraction irradiation photocyclization Crystal structure crystals diffraction irradiation photocyclization |
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Crystal structure crystals diffraction irradiation photocyclization Crystal structure crystals diffraction irradiation photocyclization Álvarez-Dorta, Dimitri León, Elisa I. Martín, Ángeles Kennedy, Alan R. Pérez-Martín, Inés Shankland, Kenneth Suárez, Ernesto Regio- and Stereoselectivity of the Norrish–Yang Photocyclization of Dialkyl 1,2-Diketones: Solution versus Solid State Photochemistry of Two Polymorphs |
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As shown by X-ray crystallography, crystals of 3β-acetoxy-16,17-seco-17,20-dioxopregn-5-ene-16-nitrile are dimorphic. The regioselectivity of the Norrish–Yang type II photocyclization under visible light of this steroidal 1,2-diketone, which bears primary, secondary, and tertiary nonequivalent abstractable γ-hydrogens, dramatically increases in the crystalline state of both polymorphs. X-ray crystallography and molecular mechanics calculations reveal crystal structure–solid state photochemistry relationships. |
author2 |
Ministerio de Economía y Competitividad (España) |
author_facet |
Ministerio de Economía y Competitividad (España) Álvarez-Dorta, Dimitri León, Elisa I. Martín, Ángeles Kennedy, Alan R. Pérez-Martín, Inés Shankland, Kenneth Suárez, Ernesto |
format |
artículo |
topic_facet |
Crystal structure crystals diffraction irradiation photocyclization |
author |
Álvarez-Dorta, Dimitri León, Elisa I. Martín, Ángeles Kennedy, Alan R. Pérez-Martín, Inés Shankland, Kenneth Suárez, Ernesto |
author_sort |
Álvarez-Dorta, Dimitri |
title |
Regio- and Stereoselectivity of the Norrish–Yang Photocyclization of Dialkyl 1,2-Diketones: Solution versus Solid State Photochemistry of Two Polymorphs |
title_short |
Regio- and Stereoselectivity of the Norrish–Yang Photocyclization of Dialkyl 1,2-Diketones: Solution versus Solid State Photochemistry of Two Polymorphs |
title_full |
Regio- and Stereoselectivity of the Norrish–Yang Photocyclization of Dialkyl 1,2-Diketones: Solution versus Solid State Photochemistry of Two Polymorphs |
title_fullStr |
Regio- and Stereoselectivity of the Norrish–Yang Photocyclization of Dialkyl 1,2-Diketones: Solution versus Solid State Photochemistry of Two Polymorphs |
title_full_unstemmed |
Regio- and Stereoselectivity of the Norrish–Yang Photocyclization of Dialkyl 1,2-Diketones: Solution versus Solid State Photochemistry of Two Polymorphs |
title_sort |
regio- and stereoselectivity of the norrish–yang photocyclization of dialkyl 1,2-diketones: solution versus solid state photochemistry of two polymorphs |
publisher |
ACS Publications |
publishDate |
2022-10-25 |
url |
http://hdl.handle.net/10261/288760 |
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