Regio- and stereoselectivity of the Norrish-Yang photocyclization of dialkyl 1,2- diketones. Solution versus solid state photochemistry of two polymorphs

Dimitri Alvarez-Dorta; Elisa I. León; Ángeles Martín; Alan R. Kennedy; Inés Pérez-Martín; Kenneth Shankland; Ernesto Suárez

doi:10.1021/acs.joc.2c01855

Regio- and stereoselectivity of the Norrish-Yang photocyclization of dialkyl 1,2- diketones. Solution versus solid state photochemistry of two polymorphs

Dimitri Alvarez-Dorta, Elisa I. León, Ángeles Martín, Alan R. Kennedy, Inés Pérez-Martín, Kenneth Shankland, Ernesto Suárez

Pure And Applied Chemistry

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5 Citations (Scopus)

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Abstract

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.

Original language	English
Pages (from-to)	14940-14947
Number of pages	8
Journal	Journal of Organic Chemistry
Volume	87
Issue number	21
Early online date	25 Oct 2022
DOIs	https://doi.org/10.1021/acs.joc.2c01855
Publication status	Published - 4 Nov 2022

Keywords

regio- and stereoselectivity
Norrish−Yang photocyclization
dialkyl 1,2-diketones
solution
solid state phytochemistry
polymorphs

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10.1021/acs.joc.2c01855Licence: CC BY 4.0

Alvarez-Dorta-JOC-2022-Regio-and-stereoselectivity-of-the-Norrish-Yang-photocyclization-of-dialkyl-1-2-diketonesFinal published version, 1.26 MBLicence: CC BY 4.0

Data for: "Regio- and stereoselectivity of the Norrish-Yang photocyclization of dialkyl 1,2- diketones. Solution versus solid state photochemistry of two polymorphs"
Alvarez-Dorta, D. (Contributor), León, E. I. (Contributor), Martín, Á. (Contributor), Kennedy, A. R. (Creator), Pérez-Martín, I. (Contributor), Shankland, K. (Contributor) & Suárez, E. (Contributor), Cambridge Crystallographic Data Centre, 13 Sept 2023
DOI: 10.5517/ccdc.csd.cc2ckh4l, https://dx.doi.org/10.5517/ccdc.csd.cc1498j7 and one more link, https://dx.doi.org/10.5517/ccdc.csd.cc1498k8 (show fewer)
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title = "Regio- and stereoselectivity of the Norrish-Yang photocyclization of dialkyl 1,2- diketones. Solution versus solid state photochemistry of two polymorphs",

abstract = "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.",

keywords = "regio- and stereoselectivity, Norrish−Yang photocyclization, dialkyl 1,2-diketones, solution, solid state phytochemistry, polymorphs",

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year = "2022",

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day = "4",

doi = "10.1021/acs.joc.2c01855",

language = "English",

volume = "87",

pages = "14940--14947",

journal = "Journal of Organic Chemistry",

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TY - JOUR

T1 - Regio- and stereoselectivity of the Norrish-Yang photocyclization of dialkyl 1,2- diketones. Solution versus solid state photochemistry of two polymorphs

AU - Alvarez-Dorta, Dimitri

AU - León, Elisa I.

AU - Martín, Ángeles

AU - Kennedy, Alan R.

AU - Pérez-Martín, Inés

AU - Shankland, Kenneth

AU - Suárez, Ernesto

PY - 2022/11/4

Y1 - 2022/11/4

N2 - 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.

AB - 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.

KW - regio- and stereoselectivity

KW - Norrish−Yang photocyclization

KW - dialkyl 1,2-diketones

KW - solution

KW - solid state phytochemistry

KW - polymorphs

U2 - 10.1021/acs.joc.2c01855

DO - 10.1021/acs.joc.2c01855

M3 - Article

SN - 0022-3263

VL - 87

SP - 14940

EP - 14947

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 21

ER -

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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Data for: "Regio- and stereoselectivity of the Norrish-Yang photocyclization of dialkyl 1,2- diketones. Solution versus solid state photochemistry of two polymorphs"

Cite this