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Twisting and Turning the Sulfonamide Bond: A Synthetic, Quantum Chemical, and Crystallographic Study
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-03-12 , DOI: 10.1021/acs.joc.9b03394 Oleksandr P. Blahun 1, 2 , Alexander B. Rozhenko 3, 4 , Eduard Rusanov 3 , Serhii Zhersh 1 , Andrey A. Tolmachev 1, 2 , Dmitriy M. Volochnyuk 1, 2, 3 , Oleksandr O. Grygorenko 1, 2
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-03-12 , DOI: 10.1021/acs.joc.9b03394 Oleksandr P. Blahun 1, 2 , Alexander B. Rozhenko 3, 4 , Eduard Rusanov 3 , Serhii Zhersh 1 , Andrey A. Tolmachev 1, 2 , Dmitriy M. Volochnyuk 1, 2, 3 , Oleksandr O. Grygorenko 1, 2
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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.
中文翻译：
扭转和扭转磺酰胺键：合成，量子化学和晶体学研究。
磺酰胺键的结构限制被用来设计具有异常几何参数的阿马他丹。根据剑桥晶体学数据库中公布的叔脂族磺酰胺叔胺的分析结果，概述了帕奎特的阿司他（即带有桥头氮原子的桥联双环阿司他），其中许多化合物（包括新颖的最小代表化合物2-thia-1-）通过将相应的氨基磺酰氟环化，合成氮杂双环[2.1.1]己烷2，2-二氧化物）。通过晶体学和量子化学方法研究了一系列叔脂族磺酰胺。发现氮孤对的s-字符是定义S–N键性质的最重要因素。因此，从sp 3开始普通磺酰胺中的β-混合孤对与最小的帕奎特苏丹娜中的sp-样孤对导致SN键长度增加约20％。0.06埃。应变能约为 预测后一种化合物为30 kcal / mol，高于研究的任何现有磺酰胺。
更新日期：2020-04-24
中文翻译：
扭转和扭转磺酰胺键：合成，量子化学和晶体学研究。
磺酰胺键的结构限制被用来设计具有异常几何参数的阿马他丹。根据剑桥晶体学数据库中公布的叔脂族磺酰胺叔胺的分析结果，概述了帕奎特的阿司他（即带有桥头氮原子的桥联双环阿司他），其中许多化合物（包括新颖的最小代表化合物2-thia-1-）通过将相应的氨基磺酰氟环化，合成氮杂双环[2.1.1]己烷2，2-二氧化物）。通过晶体学和量子化学方法研究了一系列叔脂族磺酰胺。发现氮孤对的s-字符是定义S–N键性质的最重要因素。因此，从sp 3开始普通磺酰胺中的β-混合孤对与最小的帕奎特苏丹娜中的sp-样孤对导致SN键长度增加约20％。0.06埃。应变能约为 预测后一种化合物为30 kcal / mol，高于研究的任何现有磺酰胺。
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