Bidentate Chiral Bis(imidazolium)‐Based Halogen‐Bond Donors: Synthesis and Applications in Enantioselective Recognition and Catalysis

Sutar, Revannath L.; Engelage, Elric; Stoll, Raphael; Huber, Stefan M.

doi:10.1002/anie.201915931

Cited by 92 publications

(79 citation statements)

References 64 publications

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“…Lastly, asymmetric catalysis utilizing halogen bond as a control element is starting to appear in literature [95]. We expect that many more papers may appear, and the strategy may mature to a standard protocol in organocatalysis.…”

Section: Discussionmentioning

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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Section: Discussionmentioning

confidence: 99%

Application of Halogen Bonding to Organocatalysis: A Theoretical Perspective

Hui

Wong

2020

Molecules

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“…A major break‐through in asymmetric halogen‐bond catalysis was recently reported by Huber and colleagues . The authors were able to synthesize chiral halogen‐bond donors C16 that are able to differentiate between both enantiomers of different benzylamine derivatives.…”

Section: Halogen Bondingmentioning

confidence: 99%

σ‐Hole Interactions in Catalysis

2020

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Noncovalent interactions like halogen, chalcogen, and pnictogen bonding are known for a very long time. During the last decade, these interactions have found different applications in catalysis. These forces are often called σ‐hole interactions which can be explained by the anisotropic distribution of the electron density around these atoms. In this MiniReview, we will present recent applications of halogen, chalcogen, and pnictogen bonding in catalysis and discuss experimental and computational investigations to gain more insights into the underlying mechanisms.

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“…[12] Lately, a first example has also been reported in which enantioselectivity in a Mukaiyama aldol reaction was induced by a chiral halogen bond donor devoid of any further coordinating groups. [13] The application of halogen bonding in transition metal chemistry has yet mostly been limited to halogen bonding ligands which induce organization of the ligand sphere. [14][15][16][17][18] Halogen bonds to halide [19][20][21][22] ligands as well as numerous other [23] Lewis basic ligands in metal complexes have been observed for inorganic and organic halogen bond donors.…”

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confidence: 99%

Activation of a Metal‐Halogen Bond by Halogen Bonding

et al. 2020

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In recent years, the non‐covalent interaction of halogen bonding (XB) has found increasing application in organocatalysis. However, reports of the activation of metal‐ligand bonds by XB have so far been limited to a few reactions with elemental iodine or bromine. Herein, we present the activation of metal‐halogen bonds by two classes of inert halogen bond donors and the use of the resulting activated complexes in homogenous gold catalysis. The only recently explored class of iodolium derivatives were shown to be effective activators in two test reactions and their activity could be modulated by blocking of the Lewis acidic sites. Bis(benzimidazolium)‐based halogen bonding activators provided even more rapid conversion, while the non‐iodinated reference compound showed little activity. The role of halogen bonding in the activation of metal‐halogen bonds was further investigated by NMR experiments and DFT calculations, which support the mode of activation occurring via halogen bonding.

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Bidentate Chiral Bis(imidazolium)‐Based Halogen‐Bond Donors: Synthesis and Applications in Enantioselective Recognition and Catalysis

Cited by 92 publications

References 64 publications

Application of Halogen Bonding to Organocatalysis: A Theoretical Perspective

Application of Halogen Bonding to Organocatalysis: A Theoretical Perspective

σ‐Hole Interactions in Catalysis

Activation of a Metal‐Halogen Bond by Halogen Bonding

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