Three-center-four-electron halogen bond enables non-metallic complex catalysis for Mukaiyama-Mannich-type reaction

Oishi, Shunya; Fujinami, Takeshi; MASUI, Yu; Suzuki, Toshiyasu; KATO, Masayuki; Ohtsuka, Naoya; Momiyama, Norie

doi:10.1016/j.isci.2022.105220

Cited by 12 publications

(7 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The bonding in halonium ions (X = Cl, Br, and I) leads to a hypercoordinated system. These stable − noncovalent complexes with short interatomic distances, in which the central atom exceeds the octet rule, have attracted interest due to their applicability as synthetic reagents , and in the design of complex supramolecular synthons ,− and two-dimensional (2D) halogen-bonded organic framework (XOF) materials. − The nature of the interaction in halonium cations can be described in terms of orbital and electrostatic contributions, − with smaller contribution of dispersion forces . According to the Pimentel–Rundle model, − the halonium cation interacts simultaneously with two Lewis bases by accepting electrons through both lobes of its empty p-orbital.…”

Section: Introductionmentioning

confidence: 99%

Structure and Bonding of Halonium Compounds

2023

View full text Add to dashboard Cite

The geometrical parameters and the bonding in [D···X···D]+ halonium compounds, where D is a Lewis base with N as the donor atom and X is Cl, Br, or I, have been investigated through a combined structural and computational study. Cambridge Structural Database (CSD) searches have revealed linear and symmetrical [D···X···D]+ frameworks with neutral donors. By means of density functional theory (DFT), molecular electrostatic potential (MEP), and energy decomposition analyses (EDA) calculations, we have studied the effect of various halogen atoms (X) on the [D···X···D]+ framework, the effect of different nitrogen-donor groups (D) attached to an iodonium cation (X = I), and the influence of the electron density alteration on the [D···I···D]+ halonium bond by variation of the R substituents at the N-donor upon the symmetry, strength, and nature of the interaction. The physical origin of the interaction arises from a subtle interplay between electrostatic and orbital contributions (σ-hole bond). Interaction energies as high as 45 kcal/mol suggest that halonium bonds can be exploited for the development of novel halonium transfer agents, in asymmetric halofunctionalization or as building blocks in supramolecular chemistry.

show abstract

Section: Introductionmentioning

confidence: 99%

Structure and Bonding of Halonium Compounds

2023

View full text Add to dashboard Cite

show abstract

“…In 2022, Momiyama developed a catalytic method using [N−I−N] type XB (Figure 4). [7a] The work utilized classical symmetrical [N−I−N] type XB compounds (Figure 4b) as catalysts to achieve non‐metal‐catalyzed Mukaiyama‐Mannich‐type reactions (Figure 4c) efficiently. In this catalytic reaction, the hydrogen on the sp 2 hybridized carbon in the catalyst first forms a hydrogen bond with chlorine.…”

Section: Applicationsmentioning

confidence: 99%

[N−I−N] Type Halogen Bonding: Structure, Synthesis and Applications

Wang,

Xing

2024

Eur J Org Chem

View full text Add to dashboard Cite

Halogen bond has received widespread attention in recent years due to the vast applications in supramolecular chemistry, sensing and crystal engineering. In contrast to the normal halogen bonds, [N–I–N] type halogen bond exhibits enhanced strength and solvent resistance capabilities. It adopts a bonding geometry of the three‐center four‐electron bond, where the nitrogen can be a neutral, positive, or negative species such as pyridine, saccharin, and urotropine moieties. The emerging new type halogen bond has found specific potentials in constructing supramolecular architectures and catalysis. This concept provides a brief summary based on recent developments of [N–I–N] type halogen bonding, reviewing and summarizing its synthesis, structure and application.

show abstract

“…62,77,117 Halogen(I) Catalysis. The iodine(I) and bromine(I) complexes of 1,2-bis(pyridine-2-ylethynyl)benzene accompanied by a non-nucleophilic counteranion have been proposed as anion binding catalysts for a Mukaiyama−Mannich-type reaction of N-heteroaromatics (Scheme 4) by Momiyama and co-workers, 120 providing excellent yields even with as low as 0.1% catalyst loading. The halogen(I) of the […”

Section: N Nmr Coordination Shifts Upon Formation Of [N•••i•••n] + Co...mentioning

confidence: 99%

“…The iodine(I) and bromine(I) complexes of 1,2-bis(pyridine-2-ylethynyl)benzene accompanied by a non-nucleophilic counteranion have been proposed as anion binding catalysts for a Mukaiyama–Mannich-type reaction of N -heteroaromatics (Scheme ) by Momiyama and co-workers, providing excellent yields even with as low as 0.1% catalyst loading. The halogen(I) of the [N···X···N] + complex is suggested to participate in the exchange reactions [N···X···N] + → [N···X···Cl] → [Cl···X···Cl] − → [N···X···N] + throughout the catalytic cycle, which involves the breakage and formation of three-center halogen-bond complexes.…”

Section: Applicationsmentioning

confidence: 99%

Halogen Bonds of Halogen(I) Ions─Where Are We and Where to Go?

Wieske,

Erdelyi

2023

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Halenium ions, X + , are particularly strong halogen-bond donors that interact with two Lewis bases simultaneously to form linear [D•••X•••D] + -type halonium complexes. Their three-center, four-electron halogen bond is both fundamentally interesting and technologically valuable as it tames the reactivity of halogen(I) ions, opening up new horizons in a variety of fields including synthetic organic and supramolecular chemistry. Understanding this bonding situation enables the development of improved halogen(I) transfer reactions and of advanced functional materials. Following a decade of investigations of basic principles, the range of applications is now rapidly widening. In this Perspective, we assess the status of the field and identify its key advances and the main bottlenecks. Clearing common misunderstandings that may hinder future progress, we aim to inspire and direct future research efforts.

show abstract

Three-center-four-electron halogen bond enables non-metallic complex catalysis for Mukaiyama-Mannich-type reaction

Cited by 12 publications

References 45 publications

Structure and Bonding of Halonium Compounds

Structure and Bonding of Halonium Compounds

[N−I−N] Type Halogen Bonding: Structure, Synthesis and Applications

Halogen Bonds of Halogen(I) Ions─Where Are We and Where to Go?

Contact Info

Product

Resources

About