N - To C -sulfonyl photoisomerisation of dihydropyridinones: A synthetic and mechanistic study

Pei Pei Yeh; James E. Taylor; Daniel G. Stark; David S.B. Daniels; Charlene Fallan; John C. Walton; Andrew D. Smith

doi:10.1039/c7ob01699a

N - To C -sulfonyl photoisomerisation of dihydropyridinones: A synthetic and mechanistic study

Pei Pei Yeh, James E. Taylor, Daniel G. Stark, David S.B. Daniels, Charlene Fallan, John C. Walton, Andrew D. Smith

Department of Chemistry

University of St Andrews

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

13 Citations (SciVal)

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
Number of pages	9
Journal	Organic and Biomolecular Chemistry
Volume	15
Issue number	42
Early online date	16 Oct 2017
DOIs	https://doi.org/10.1039/c7ob01699a
Publication status	Published - 14 Nov 2017

Funding

We 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. We also thank the EPSRC UK National Mass Spectrometry Facility at Swansea University.

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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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.",

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T2 - A synthetic and mechanistic study

AU - Yeh, Pei Pei

AU - Taylor, James E.

AU - Stark, Daniel G.

AU - Daniels, David S.B.

AU - Fallan, Charlene

AU - Walton, John C.

AU - Smith, Andrew D.

PY - 2017/11/14

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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.

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N - To C -sulfonyl photoisomerisation of dihydropyridinones: A synthetic and mechanistic study

Abstract

Funding

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