Hypervalent Iodine(III) Compounds as Biaxial Halogen Bond Donors

Heinen, Flemming; Engelage, Elric; Cramer, Christopher J.; Huber, Stefan M.

doi:10.1021/jacs.9b13309

Cited by 92 publications

(95 citation statements)

References 55 publications

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“…The importance of the pentynyl linker, together with the requirement for the benzoyl ester, suggest a highly preorganised structure [ 55 ] in which the carbonyl group functions as a tempered Lewis base upon ligand exchange ( Fig. 5 ) [ 56 ]. This working hypothesis may also rationalise the deletion experiment ( 10 ), the recalcitrance of acetyl derivatives, and the striking reactivity disparity between amides ( 12 / 13 ) and the phthalimide derivative 16 .…”

Section: Resultsmentioning

confidence: 99%

Fluorohydration of alkynes via I(I)/I(III) catalysis

Neufeld¹,

Daniliuc²,

Gilmour³

2020

Beilstein J. Org. Chem.

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Substrate specificity is ubiquitous in biological catalysis, but less pervasive in the realm of small-molecule catalysis. Herein, we disclose an intriguing example of substrate specificity that was observed whilst exploring catalysis-based routes to generate α-fluoroketones from terminal and internal alkynes under the auspices of I(I)/I(III) catalysis. Utilising p-TolI as an inexpensive organocatalyst with Selectfluor® and amine/HF mixtures, the formation of protected α-fluoroketones from simple alkynes was realised. Whilst the transient p-TolIF2 species generated in situ productively engaged with pentynyl benzoate scaffolds to generate the desired α-fluoroketone motif, augmentation or contraction of the linker suppressed catalysis. The prerequisite for this substructure was established by molecular editing and was complemented with a physical organic investigation of possible determinants.

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Section: Resultsmentioning

confidence: 99%

Fluorohydration of alkynes via I(I)/I(III) catalysis

Neufeld¹,

Daniliuc²,

Gilmour³

2020

Beilstein J. Org. Chem.

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“…Kirshenboim and Kozuch [ 89 ] explored this scenario, and the manner in which the multiple σ-holes might affect the halogen bonding. Heinen et al [ 90 ] later documented these ideas in the particular case of the hypervalent I atom through both experimental and computational means. The ability of a single Lewis acid atom with multiple σ-holes to engage in several noncovalent bonds has been explored also in the framework of chalcogen, pnicogen, and tetrel bonds [ 91 , 92 , 93 , 94 , 95 , 96 , 97 ].…”

Section: Discussionmentioning

confidence: 99%

Comparison of Bifurcated Halogen with Hydrogen Bonds

Scheiner

2021

Molecules

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Bifurcated halogen bonds are constructed with FBr and FI as Lewis acids, paired with NH3 and NCH bases. The first type considered places two bases together with a single acid, while the reverse case of two acids sharing a single base constitutes the second type. These bifurcated systems are compared with the analogous H-bonds wherein FH serves as the acid. In most cases, a bifurcated system is energetically inferior to a single linear bond. There is a larger energetic cost to forcing the single σ-hole of an acid to interact with a pair of bases, than the other way around where two acids engage with the lone pair of a single base. In comparison to FBr and FI, the H-bonding FH acid is better able to participate in a bifurcated sharing with two bases. This behavior is traced to the properties of the monomers, in particular the specific shape of the molecular electrostatic potential, the anisotropy of the orbitals of the acid and base that interact directly with one another, and the angular extent of the total electron density of the two molecules.

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“…Thus, only catalytic quantities of iodoarenes are needed. As the coordination patterns in hypervalent iodine species can be viewed as special cases of halogen bonding (Heinen et al, 2020;Turunen and Erdélyi, 2020) and as XBs can contribute to halogen insertions, it is pertinent to mention this type of catalysis in the review. Nevertheless, the contribution of XBs to these catalytic processes are again rarely acknowledged and the topic has been thoroughly reviewed in recent years by experts in the field.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Halogen Bonds in Asymmetric Catalysis

Kaasik

Kanger

2020

Front. Chem.

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Halogen bonding has received a significant increase in attention in the past 20 years. An important part of this interest has centered on catalytic applications of halogen bonding. Halogen bond (XB) catalysis is still a developing field in organocatalysis, although XB catalysis has outgrown its proof of concept phase. The start of this year witnessed the publication of the first example of a purely XB-based enantioselective catalytic reaction. While the selectivity can be improved upon, there are already plenty of examples in which halogen bonds, among other interactions, play a crucial role in the outcome of highly enantioselective reactions. This paper will give an overview of the current state of the use of XBs in catalytic stereoselective processes.

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Hypervalent Iodine(III) Compounds as Biaxial Halogen Bond Donors

Cited by 92 publications

References 55 publications

Fluorohydration of alkynes via I(I)/I(III) catalysis

Fluorohydration of alkynes via I(I)/I(III) catalysis

Comparison of Bifurcated Halogen with Hydrogen Bonds

Supramolecular Halogen Bonds in Asymmetric Catalysis

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