The Photochemical Mediated Ring Contraction of 4H-1,2,6-Thiadiazines To Afford 1,2,5-Thiadiazol-3(2H)-one 1-Oxides

Emmanouil Broumidis; Christopher G. Thomson; Brendan Gallagher; Lia Sotorríos; Kenneth G. McKendrick; Stuart A. Macgregor; Martin J. Paterson; Janet E. Lovett; Gareth O. Lloyd; Georgina M. Rosair; Andreas S. Kalogirou; Panayiotis A. Koutentis; Filipe Vilela

doi:10.1021/acs.orglett.3c02673

The Photochemical Mediated Ring Contraction of 4H-1,2,6-Thiadiazines To Afford 1,2,5-Thiadiazol-3(2H)-one 1-Oxides

Emmanouil Broumidis, Christopher G. Thomson, Brendan Gallagher, Lia Sotorríos, Kenneth G. McKendrick, Stuart A. Macgregor, Martin J. Paterson, Janet E. Lovett, Gareth O. Lloyd, Georgina M. Rosair, Andreas S. Kalogirou, Panayiotis A. Koutentis, Filipe Vilela

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Abstract

1,2,6-Thiadiazines treated with visible light and ³O ₂ under ambient conditions are converted into difficult-to-access 1,2,5-thiadiazole 1-oxides (35 examples, yields of 39-100%). Experimental and theoretical studies reveal that 1,2,6-thiadiazines act as triplet photosensitizers that produce ¹O ₂ and then undergo a chemoselective [3 + 2] cycloaddition to give an endoperoxide that ring contracts with selective carbon atom excision and complete atom economy. The reaction was optimized under both batch and continuous-flow conditions and is also efficient in green solvents.

Original language	English
Pages (from-to)	6907–6912
Number of pages	6
Journal	Organic Letters
Volume	25
Issue number	37
Early online date	11 Sept 2023
DOIs	https://doi.org/10.1021/acs.orglett.3c02673
Publication status	Published - 22 Sept 2023

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Broumidis, E., Thomson, C. G., Gallagher, B., Sotorríos, L., McKendrick, K. G., Macgregor, S. A., Paterson, M. J., Lovett, J. E., Lloyd, G. O., Rosair, G. M., Kalogirou, A. S., Koutentis, P. A., & Vilela, F. (2023). The Photochemical Mediated Ring Contraction of 4H-1,2,6-Thiadiazines To Afford 1,2,5-Thiadiazol-3(2H)-one 1-Oxides. Organic Letters, 25(37), 6907–6912. https://doi.org/10.1021/acs.orglett.3c02673

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title = "The Photochemical Mediated Ring Contraction of 4H-1,2,6-Thiadiazines To Afford 1,2,5-Thiadiazol-3(2H)-one 1-Oxides",

abstract = "1,2,6-Thiadiazines treated with visible light and 3O 2 under ambient conditions are converted into difficult-to-access 1,2,5-thiadiazole 1-oxides (35 examples, yields of 39-100%). Experimental and theoretical studies reveal that 1,2,6-thiadiazines act as triplet photosensitizers that produce 1O 2 and then undergo a chemoselective [3 + 2] cycloaddition to give an endoperoxide that ring contracts with selective carbon atom excision and complete atom economy. The reaction was optimized under both batch and continuous-flow conditions and is also efficient in green solvents.",

author = "Emmanouil Broumidis and Thomson, {Christopher G.} and Brendan Gallagher and Lia Sotorr{\'i}os and McKendrick, {Kenneth G.} and Macgregor, {Stuart A.} and Paterson, {Martin J.} and Lovett, {Janet E.} and Lloyd, {Gareth O.} and Rosair, {Georgina M.} and Kalogirou, {Andreas S.} and Koutentis, {Panayiotis A.} and Filipe Vilela",

year = "2023",

month = sep,

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doi = "10.1021/acs.orglett.3c02673",

language = "English",

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journal = "Organic Letters",

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Broumidis, E, Thomson, CG, Gallagher, B, Sotorríos, L, McKendrick, KG, Macgregor, SA, Paterson, MJ, Lovett, JE, Lloyd, GO, Rosair, GM, Kalogirou, AS, Koutentis, PA & Vilela, F 2023, 'The Photochemical Mediated Ring Contraction of 4H-1,2,6-Thiadiazines To Afford 1,2,5-Thiadiazol-3(2H)-one 1-Oxides', Organic Letters, vol. 25, no. 37, pp. 6907–6912. https://doi.org/10.1021/acs.orglett.3c02673

TY - JOUR

T1 - The Photochemical Mediated Ring Contraction of 4H-1,2,6-Thiadiazines To Afford 1,2,5-Thiadiazol-3(2H)-one 1-Oxides

AU - Broumidis, Emmanouil

AU - Thomson, Christopher G.

AU - Gallagher, Brendan

AU - Sotorríos, Lia

AU - McKendrick, Kenneth G.

AU - Macgregor, Stuart A.

AU - Paterson, Martin J.

AU - Lovett, Janet E.

AU - Lloyd, Gareth O.

AU - Rosair, Georgina M.

AU - Kalogirou, Andreas S.

AU - Koutentis, Panayiotis A.

AU - Vilela, Filipe

PY - 2023/9/22

Y1 - 2023/9/22

N2 - 1,2,6-Thiadiazines treated with visible light and 3O 2 under ambient conditions are converted into difficult-to-access 1,2,5-thiadiazole 1-oxides (35 examples, yields of 39-100%). Experimental and theoretical studies reveal that 1,2,6-thiadiazines act as triplet photosensitizers that produce 1O 2 and then undergo a chemoselective [3 + 2] cycloaddition to give an endoperoxide that ring contracts with selective carbon atom excision and complete atom economy. The reaction was optimized under both batch and continuous-flow conditions and is also efficient in green solvents.

AB - 1,2,6-Thiadiazines treated with visible light and 3O 2 under ambient conditions are converted into difficult-to-access 1,2,5-thiadiazole 1-oxides (35 examples, yields of 39-100%). Experimental and theoretical studies reveal that 1,2,6-thiadiazines act as triplet photosensitizers that produce 1O 2 and then undergo a chemoselective [3 + 2] cycloaddition to give an endoperoxide that ring contracts with selective carbon atom excision and complete atom economy. The reaction was optimized under both batch and continuous-flow conditions and is also efficient in green solvents.

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JO - Organic Letters

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The Photochemical Mediated Ring Contraction of 4H-1,2,6-Thiadiazines To Afford 1,2,5-Thiadiazol-3(2H)-one 1-Oxides

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