Sulfonamidyls. 5. Electron spin resonance spectroscopic evidence for four- and five-membered-ring sulfonamidyls and sulfonyl nitroxides

Teeninga, Herman; Engberts, Jan B. F. N.

doi:10.1021/jo00152a024

Cited by 31 publications

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“…Pyramidalization at sulfur and (at least in the solid state) also on nitrogen is reflected in the 1 H NMR data of the products. A pyramidal array around the N-atom may well be prevailing also in solution since there is strong indication that electron attracting atoms or groups being not conjugated to the N lone pair stabilize a pyramidal configuration at the N atom in heterocycles [21][22][23].…”

Section: Formal Oxygen Migrationmentioning

confidence: 99%

The surprising photochemistry of sultams related to saccharin

Döpp¹

2001

International Journal of Photoenergy

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The known light induced reactions of sulfonamides and sultams are in most (but not all) cases initiated by S–N homolysis. Sulfur dioxide release may be a consequence of this primary process. In the author's laboratory three hitherto unexplored photoreactions of saccharin-derived sultams have been investigated: (i) a novel formal oxygen shift from sulfur to nitrogen generating upto now unknown cyclic N-hydroxysulfinamides; (ii) a condensative dimerization of 2,3-dihydro-1,2- benzoisothiazole 1,1-dioxide generating a new cleft molecule, and (iii) a facile allylic skeletal rearrangement of a pyrrolo-anellated dihydro- 1,2-benzoisothiazole. At least in the latter two cases an initial S–N-homolysis seems to be vital for the processes observed, whereas in the first case some ambiguity remains with respect to the first step. Scope and limitations are discussed and rationales for the conversions observed are presented, with special emphasis on structure proof by X-ray crystal structure determinations. All reactions discussed have to be treated within the wider context of current sulfonamide and sultam photochemistry.

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Section: Formal Oxygen Migrationmentioning

confidence: 99%

The surprising photochemistry of sultams related to saccharin

Döpp¹

2001

International Journal of Photoenergy

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“…The structures of all other products could then be safely assigned on the basis of close analogies in the 1 H NMR, IR and mass spectra. The 1 H NMR data clearly reflect the build-up of new stereogenic centers at sulfur (albeit of moderate stability) and on nitrogen (relevant at least for the solid state but there is strong indication that electron demanding atoms or groups being not in conjugation with the nitrogen lone pair stabilize a pyramidal configuration of N atoms in heterocycles [12][13][14][15] ).…”

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confidence: 95%

Photoisomerization of Sultams Derived from Saccharin; Part 4: Generation of Cyclic Sulfine Hydroxamic Acids

Döpp¹,

Lauterfeld²,

Schneider³

et al. 2004

Synthesis

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Various areno[d]annulated 3-mono-and 3,3-disubstituted 2,3-dihydro-[1,2]benzisothiazole 1,1-dioxides undergo a facile rearrangement into the corresponding 2,3-dihydro-2-hydroxy-[1,2]benzisothiazole 1-oxides upon irradiation at 254 nm in methanol. The latter represent a new, but labile functional group, i.e. the cyclic version of the sulfine hydroxamic acid. When C-3 in the starting materials is substituted by one methyl or phenyl only, that photoisomer is formed preferentially which has the sulfoxide O atom in an anti-orientation to the said substituent. 2-Alkoxymethyl substituted starting materials show the same type of formal oxygen shift. The structures of all photoproducts have been assigned largely from 1 H NMR data and unambiguously corroborated by X-ray crystal structure analyses of two photoproducts.

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Four‐Membered Sulfur Heterocycles

Dittmer

Sedergran

1985

Chemistry of Heterocyclic Compounds: A Series of Monographs

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Sulfonamidyls. 5. Electron spin resonance spectroscopic evidence for four- and five-membered-ring sulfonamidyls and sulfonyl nitroxides

Cited by 31 publications

References 0 publications

The surprising photochemistry of sultams related to saccharin

The surprising photochemistry of sultams related to saccharin

Photoisomerization of Sultams Derived from Saccharin; Part 4: Generation of Cyclic Sulfine Hydroxamic Acids

Four‐Membered Sulfur Heterocycles

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