Twisting and Turning the Sulfonamide Bond: A Synthetic, Quantum Chemical, and Crystallographic Study
- Oleksandr P. Blahun
Oleksandr P. BlahunEnamine Ltd., Chervonotkatska Street 78, Kyiv 02094, UkraineTaras Shevchenko National University of Kyiv, Volodymyrska Street 60, Kyiv 01601, UkraineMore by Oleksandr P. Blahun
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- Alexander B. Rozhenko
Alexander B. RozhenkoInstitute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanska Street 5, Kyiv 02660, UkraineNational Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Peremogy Avenue 37, Kyiv 03056, UkraineMore by Alexander B. Rozhenko
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- Eduard Rusanov
Eduard RusanovInstitute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanska Street 5, Kyiv 02660, UkraineMore by Eduard Rusanov
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- Serhii Zhersh
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- Andrey A. Tolmachev
Andrey A. TolmachevEnamine Ltd., Chervonotkatska Street 78, Kyiv 02094, UkraineTaras Shevchenko National University of Kyiv, Volodymyrska Street 60, Kyiv 01601, UkraineMore by Andrey A. Tolmachev
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- Dmitriy M. Volochnyuk
Dmitriy M. VolochnyukEnamine Ltd., Chervonotkatska Street 78, Kyiv 02094, UkraineTaras Shevchenko National University of Kyiv, Volodymyrska Street 60, Kyiv 01601, UkraineInstitute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanska Street 5, Kyiv 02660, UkraineMore by Dmitriy M. Volochnyuk
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- Oleksandr O. Grygorenko*
Oleksandr O. Grygorenko*Email: [email protected]Enamine Ltd., Chervonotkatska Street 78, Kyiv 02094, UkraineTaras Shevchenko National University of Kyiv, Volodymyrska Street 60, Kyiv 01601, UkraineMore by Oleksandr O. Grygorenko
Abstract
Structural restriction of the sulfonamide bond was used to design sultams with abnormal geometric parameters. Based on analysis of tertiary aliphatic sulfonamides published in the Cambridge crystallographic database, Paquette’s sultams (i.e., bridged bicyclic sultams with a bridgehead nitrogen atom) were outlined, and a number of these compounds (including the novel smallest representative, 2-thia-1-azabicyclo[2.1.1]hexane 2,2-dioxide) were synthesized by cyclization of the corresponding amino sulfonyl fluorides. A series of tertiary aliphatic sulfonamides was studied by crystallographic and quantum chemical methods. It was found that the s-character of the nitrogen lone pair is the most important factor defining properties of the S–N bond. Thus, going from the sp3-hybrid lone pair in common sulfonamides to the sp-like lone pair in the smallest Paquette’s sultam resulted in an increase in S–N bond length by ca. 0.06 Å. The strain energy of ca. 30 kcal/mol was predicted for the latter compound, which was higher than for any existing sulfonamides studied.
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