Catalysis of Organic Reactions through Halogen Bonding

Sutar, Revannath L.; Huber, Stefan M.

doi:10.1021/acscatal.9b02894

Cited by 361 publications

(294 citation statements)

References 185 publications

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“…With respect to halogen bond based organocatalysis, fewer examples are known compared to anion recognition, although the number is steadily increasing . First studies were published in the early 2000 s reporting quinoline reductions and halide abstraction reactions by Bolm et al.…”

Section: Introductionmentioning

confidence: 99%

Preorganization: A Powerful Tool in Intermolecular Halogen Bonding in Solution

2020

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Preorganization is a powerful tool in supramolecular chemistry which has been utilized successfully in intra‐ and intermolecular halogen bonding. In previous work, we had developed a bidentate bis(iodobenzimidazolium)‐based halogen bond donor which featured a central trifluoromethyl substituent. This compound showed a markedly increased catalytic activity compared to unsubstituted bis(iodoimidazolium)‐based Lewis acids, which could be explained either by electronic effects (the electron withdrawal by the fluorinated substituent) or by preorganization (the hindered rotation of the halogen bonding moieties). Herein, we systematically investigate the origin of this increased Lewis acidity via a comparison of the two types of compounds and their respective derivatives with or without the central trifluoromethyl group. Calorimetric measurements of halide complexations indicated that preorganization is the main reason for the higher halogen bonding strength. The performance of the catalysts in a series of benchmark reactions corroborates this finding.

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Section: Introductionmentioning

confidence: 99%

Preorganization: A Powerful Tool in Intermolecular Halogen Bonding in Solution

2020

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“…This led to the development of new methods in organic synthesis, e.g., nucleophilic substitution/addition, cyclization, and transfer hydrogenation reactions. Several recent excellent reviews were published on the experimental studies on XB organocatalysis [17,18]. As this review focuses on the computational studies on XB organocatalysis, we do not discuss the experimental studies in detail and ask the readers to read these reviews to appreciate the progress in recent years.…”

Section: Introductionmentioning

confidence: 99%

Application of Halogen Bonding to Organocatalysis: A Theoretical Perspective

Hui

Wong

2020

Molecules

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The strong, specific, and directional halogen bond (XB) is an ideal supramolecular synthon in crystal engineering, as well as rational catalyst and drug design. These attributes attracted strong growing interest in halogen bonding in the past decade and led to a wide range of applications in materials, biological, and catalysis applications. Recently, various research groups exploited the XB mode of activation in designing halogen-based Lewis acids in effecting organic transformation, and there is continual growth in this promising area. In addition to the rapid advancements in methodology development, computational investigations are well suited for mechanistic understanding, rational XB catalyst design, and the study of intermediates that are unstable when observed experimentally. In this review, we highlight recent computational studies of XB organocatalytic reactions, which provide valuable insights into the XB mode of activation, competing reaction pathways, effects of solvent and counterions, and design of novel XB catalysts.

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“…As expected from the Ka values, the Se compound 2 was more active than its S analog 1. Therefore, the study was mainly focused on the use of 2 in comparison with reference compounds where the SeC 6 F 5 group was replaced by CH 3 (12), CH 2 C 6 F 5 (13), and I (3). The reference compound 12 without a σor π-hole donor in 3-position was chosen so as to keep the torsional angle between the two pyridine rings similar to compound 2 in order to conserve the same geometry and to analyze only the effect due to the presence of the SeC 6 F 5 group.…”

Section: Discussionmentioning

confidence: 99%

“…After concentration, the crude was purified by chromatography on silica gel (20% dichloromethane/pentane) and, if necessary, a flash column chromatography was used to remove impurities (2% ethylacetate/cyclohexane). 13 Under argon atmosphere, a 25 mL Schlenck tube was filled with copper powder (2 eq.) and anhydrous NMP (1-3 mL).…”

Section: Generalmentioning

confidence: 99%

“…Among the applications based on σ-hole interactions in solution, catalysis represents an active research area. While several catalysts acting as XB donor have been described during the last decade [6,13,14], the first examples of ChB-based catalysis have been very recently reported by the groups of Matile [15][16][17][18], Huber [19][20][21], and Wang [22]. Other recent applications of ChB concern anion binding [ 23,24] and transport [25][26][27].…”

Section: Introductionmentioning

confidence: 99%

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Chiral Chalcogen Bond Donors Based on the 4,4′-Bipyridine Scaffold

et al. 2019

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Organocatalysis through chalcogen bonding (ChB) is in its infancy, as its proof-of-principle was only reported in 2016. Herein, we report the design and synthesis of new chiral ChB donors, as well as the catalytic activity evaluation of the 5,5′-dibromo-2,2′-dichloro-3-((perfluorophenyl)selanyl)-4,4′-bipyridine as organocatalyst. The latter is based on the use of two electron-withdrawing groups, a pentafluorophenyl ring and a tetrahalo-4,4′-bipyridine skeleton, as substituents at the selenium center. Atropisomery of the tetrahalo-4,4′-bipyridine motif provides a chiral environment to these new ChB donors. Their synthesis was achieved through either selective lithium exchange and trapping or a site-selective copper-mediated reaction. Pure enantiomers of the 3-selanyl-4,4′-bipyridine were obtained by high performance liquid chromatography enantioseparation on specific chiral stationary phase, and their absolute configuration was assigned by comparison of the measured and calculated electronic circular dichroism spectra. The capability of the selenium compound to participate in σ-hole-based interactions in solution was studied by 19F NMR. Even if no asymmetric induction has been observed so far, the new selenium motif proved to be catalytically active in the reduction of 2-phenylquinoline by Hantzsch ester.

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Catalysis of Organic Reactions through Halogen Bonding

Cited by 361 publications

References 185 publications

Preorganization: A Powerful Tool in Intermolecular Halogen Bonding in Solution

Preorganization: A Powerful Tool in Intermolecular Halogen Bonding in Solution

Application of Halogen Bonding to Organocatalysis: A Theoretical Perspective

Chiral Chalcogen Bond Donors Based on the 4,4′-Bipyridine Scaffold

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