Synthesis and conformational analysis of pyran inter-halide analogues of ᴅ-talose.

IF 2.2 4区 化学 Q2 CHEMISTRY, ORGANIC Beilstein Journal of Organic Chemistry Pub Date : 2024-09-27 eCollection Date: 2024-01-01 DOI:10.3762/bjoc.20.208
Olivier Lessard, Mathilde Grosset-Magagne, Paul A Johnson, Denis Giguère
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Abstract

In this work, we describe the synthesis of halogenated pyran analogues of ᴅ-talose using a halo-divergent strategy from known 1,6-anhydro-2,3-dideoxy-2,3-difluoro-β-ᴅ-mannopyranose. In solution and in the solid-state, all analogues adopt standard 4 C 1-like conformations despite 1,3-diaxial repulsion between the F2 and the C4 halogen. Moreover, the solid-state conformational analysis of halogenated pyrans reveals deviation in the intra-annular torsion angles arising from repulsion between the axial fluorine at C2 and the axial halogen at C4, which increases with the size of the halogen at C4 (F < Cl < Br < I). Crystal packing arrangements of pyran inter-halides show hydrogen bond acceptor and nonbonding interactions for the halogen at C4. Finally, density functional theory (DFT) calculations corroborate the preference of talose analogues to adopt a 4 C 1-like conformation and a natural bonding orbital (NBO) analysis demonstrates the effects of hyperconjugation from C-F antibonding orbitals.

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ᴅ-塔罗糖吡喃间卤化物类似物的合成和构象分析。
在这项工作中,我们介绍了利用卤素发散策略,从已知的 1,6-脱氢-2,3-二脱氧-2,3-二氟-β-ᴅ-吡喃甘露糖合成了ᴅ-塔罗糖的卤代吡喃类似物。在溶液和固态中,尽管 F2 和 C4 卤素之间存在 1,3- 轴向排斥,但所有类似物都采用了类似 4 C 1 的标准构象。此外,对卤代吡喃的固态构象分析表明,由于 C2 处的轴向氟和 C4 处的轴向卤素之间存在斥力,导致环内扭转角出现偏差,这种偏差随 C4 处卤素的大小而增大(F < Cl < Br < I)。吡喃卤化物的晶体堆积排列显示了 C4 处卤素的氢键受体和非键相互作用。最后,密度泛函理论(DFT)计算证实了滑石粉类似物倾向于采用类似 4 C 1 的构象,自然成键轨道(NBO)分析表明了 C-F 反键轨道的超共轭效应。
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来源期刊
CiteScore
4.90
自引率
3.70%
发文量
167
审稿时长
1.4 months
期刊介绍: The Beilstein Journal of Organic Chemistry is an international, peer-reviewed, Open Access journal. It provides a unique platform for rapid publication without any charges (free for author and reader) – Platinum Open Access. The content is freely accessible 365 days a year to any user worldwide. Articles are available online immediately upon publication and are publicly archived in all major repositories. In addition, it provides a platform for publishing thematic issues (theme-based collections of articles) on topical issues in organic chemistry. The journal publishes high quality research and reviews in all areas of organic chemistry, including organic synthesis, organic reactions, natural product chemistry, structural investigations, supramolecular chemistry and chemical biology.
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