N- to C-sulfonyl photoisomerisation of dihydropyridinones: a synthetic and mechanistic study

Pei-Pei Yeh; James Edward Taylor; Daniel Graham Stark; David Sydney Bernard Daniels; Charlene Fallan; John Christopher Walton; Andrew David Smith

doi:10.1039/C7OB01699A

N- to C-sulfonyl photoisomerisation of dihydropyridinones: a synthetic and mechanistic study

Pei-Pei Yeh, James Edward Taylor, Daniel Graham Stark, David Sydney Bernard Daniels, Charlene Fallan, John Christopher Walton, Andrew David Smith

Research output: Contribution to journal › Article › peer-review

Abstract

The scope and limitations of a photoinitiated N- to C-sulfonyl migration process within a range of dihydropyridinones is assessed. This sulfonyl transfer proceeds without erosion of either diastereo- or enantiocontrol, and is general across a range of N-sulfonyl substituents (SO₂R; R = Ph, 4-MeC₆H₄, 4-MeOC₆H₄, 4-NO₂C₆H₄, Me, Et) as well as C(3)-(aryl, heteroaryl, alkyl and alkenyl) and C(4)-(aryl and ester) substitution. Crossover reactions indicate an intermolecular step is operative within the formal migration process, although no crossover from C-sulfonyl products was observed. EPR studies indicate the intermediacy of a sulfonyl radical and a mechanism is proposed based upon these observations.

Original language	English
Pages (from-to)	8914-8922
Journal	Organic & Biomolecular Chemistry
Volume	15
Issue number	42
Early online date	16 Oct 2017
DOIs	https://doi.org/10.1039/C7OB01699A
Publication status	E-pub ahead of print - 16 Oct 2017

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10.1039/C7OB01699ALicence: CC BY

Smith_2017_OBC_n-c-sulfonyl_CCBY-VoR
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@article{daca5ef17726428a864d578d85a47c6f,

title = "N- to C-sulfonyl photoisomerisation of dihydropyridinones: a synthetic and mechanistic study",

abstract = "The scope and limitations of a photoinitiated N- to C-sulfonyl migration process within a range of dihydropyridinones is assessed. This sulfonyl transfer proceeds without erosion of either diastereo- or enantiocontrol, and is general across a range of N-sulfonyl substituents (SO2R; R = Ph, 4-MeC6H4, 4-MeOC6H4, 4-NO2C6H4, Me, Et) as well as C(3)-(aryl, heteroaryl, alkyl and alkenyl) and C(4)-(aryl and ester) substitution. Crossover reactions indicate an intermolecular step is operative within the formal migration process, although no crossover from C-sulfonyl products was observed. EPR studies indicate the intermediacy of a sulfonyl radical and a mechanism is proposed based upon these observations.",

author = "Pei-Pei Yeh and Taylor, {James Edward} and Stark, {Daniel Graham} and Daniels, {David Sydney Bernard} and Charlene Fallan and Walton, {John Christopher} and Smith, {Andrew David}",

note = "The authors thank the European Research Council under the European Union{\textquoteright}s Seventh Framework Programme (FP7/2007–2013) ERC Grant Agreement no. 279850 (CF and JET) and EPSRC grant number EP/J018139/1 (DSBD) for funding. ADS thanks the Royal Society for a Wolfson Research Merit Award.",

year = "2017",

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doi = "10.1039/C7OB01699A",

language = "English",

volume = "15",

pages = "8914--8922",

journal = "Organic & Biomolecular Chemistry",

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TY - JOUR

T1 - N- to C-sulfonyl photoisomerisation of dihydropyridinones

T2 - a synthetic and mechanistic study

AU - Yeh, Pei-Pei

AU - Taylor, James Edward

AU - Stark, Daniel Graham

AU - Daniels, David Sydney Bernard

AU - Fallan, Charlene

AU - Walton, John Christopher

AU - Smith, Andrew David

N1 - The authors thank the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007–2013) ERC Grant Agreement no. 279850 (CF and JET) and EPSRC grant number EP/J018139/1 (DSBD) for funding. ADS thanks the Royal Society for a Wolfson Research Merit Award.

PY - 2017/10/16

Y1 - 2017/10/16

N2 - The scope and limitations of a photoinitiated N- to C-sulfonyl migration process within a range of dihydropyridinones is assessed. This sulfonyl transfer proceeds without erosion of either diastereo- or enantiocontrol, and is general across a range of N-sulfonyl substituents (SO2R; R = Ph, 4-MeC6H4, 4-MeOC6H4, 4-NO2C6H4, Me, Et) as well as C(3)-(aryl, heteroaryl, alkyl and alkenyl) and C(4)-(aryl and ester) substitution. Crossover reactions indicate an intermolecular step is operative within the formal migration process, although no crossover from C-sulfonyl products was observed. EPR studies indicate the intermediacy of a sulfonyl radical and a mechanism is proposed based upon these observations.

AB - The scope and limitations of a photoinitiated N- to C-sulfonyl migration process within a range of dihydropyridinones is assessed. This sulfonyl transfer proceeds without erosion of either diastereo- or enantiocontrol, and is general across a range of N-sulfonyl substituents (SO2R; R = Ph, 4-MeC6H4, 4-MeOC6H4, 4-NO2C6H4, Me, Et) as well as C(3)-(aryl, heteroaryl, alkyl and alkenyl) and C(4)-(aryl and ester) substitution. Crossover reactions indicate an intermolecular step is operative within the formal migration process, although no crossover from C-sulfonyl products was observed. EPR studies indicate the intermediacy of a sulfonyl radical and a mechanism is proposed based upon these observations.

UR - http://www.rsc.org/suppdata/c7/ob/c7ob01699a/c7ob01699a1.pdf

U2 - 10.1039/C7OB01699A

DO - 10.1039/C7OB01699A

M3 - Article

SN - 1477-0520

VL - 15

SP - 8914

EP - 8922

JO - Organic & Biomolecular Chemistry

JF - Organic & Biomolecular Chemistry

IS - 42

ER -

N- to C-sulfonyl photoisomerisation of dihydropyridinones: a synthetic and mechanistic study

Abstract

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Clean catalysis for sustainable develop: Clean catalysis for sustainable development

Clean catalysis for sustainable develop: Clean catalysis for sustainable development

ERC Starting Grant EnolCat: Emulating nature: Reaction diversity and understanding through asymmetric catalysis

Data underpinning: N- to C-Sulfonyl Photoisomerisation of Dihydropyridinones: A Synthetic and Mechanistic Study

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N- to C-sulfonyl photoisomerisation of dihydropyridinones: a synthetic and mechanistic study

Abstract

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Other files and links

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Projects

Clean catalysis for sustainable develop: Clean catalysis for sustainable development

Clean catalysis for sustainable develop: Clean catalysis for sustainable development

ERC Starting Grant EnolCat: Emulating nature: Reaction diversity and understanding through asymmetric catalysis

Datasets

Data underpinning: N- to C-Sulfonyl Photoisomerisation of Dihydropyridinones: A Synthetic and Mechanistic Study

Cite this