The role of halogen bonds in the catalytic mechanism of the iso-Nazarov cyclization reaction: a DFT study

Abstract

With the continuous development of halogen bonds, the halogen bond donors have been used as clean and efficient catalysts in organic reactions. In this work, inorganic halides (I2, IBr, ICl,...

Halogen Bond Catalysis: A Physical Chemistry Perspective

“…From Figure a, [1,4]-H shift included two pathways: the hydrogen/halogen bonds cocatalysis and the one-step water cocatalysis, and the Δ G values of the hydrogen/halogen bonds cocatalysis were lower than that of the one-step water cocatalysis. As shown in Figure b, I···O XB could be formed in COM1, and I···O halogen bond and H···Cl hydrogen bond could be formed in COM2-2; therefore, the hydrogen/halogen bonds cocatalysis promoted [1,4]-H shift …”

“…b: Contour line diagram of the ρ b of ICl 3 –COM1, ∇ 2 ρ b , and the ρ b of ICl 3 COM2-2. Adapted with permission from Figures 3, 7, and 9b in ref . Copyright 2022 Royal Society of Chemistry.…”

Rational Supramolecular Strategy via Halogen Bonding for Effective Halogen Recognition in Molecular Imprinting

“…The higher affinity on EDGMA-polymer was probably attributable to the lone pair of carbonyl oxygen atoms, a potential halogen bonding acceptor. 41,56 In fact, carbonyl oxygen atoms and ether oxygen atoms could act as a reliable halogen-bonding acceptors in the presence of a nitrogen atom. 57 The affinity for DVB-polymer was contrarily negligible, although our previous report suggested that aromatic rings could also act as a halogen bond acceptors.…”

Neutral Monodentate and Hypervalent Chalcogen Bond Catalysis on the Intramolecular Rauhut‐Currier Reaction of Bis(enones): A DFT Study

“…Constructing efficient and practical carbon‐carbon bonds has always been the goal of scientists, and it still occupies a priority position in the field of organic chemistry. There are many reactions to construct carbon‐carbon bonds, such as Michael addition reaction, Diels‐Alder reaction, Friedel‐Crafts reaction, Nazarov cyclization reaction, Mukaiyama aldol condensation reaction [20–23] . The Rauhut‐Currier (RC) reaction is also an important basic reaction for the efficient construction of carbon‐carbon bonds, [24–26] and which can be traced back to a US patent by Rauhut, M and Currier, H [27] in 1963.…”

“…There are many reactions to construct carbon-carbon bonds, such as Michael addition reaction, Diels-Alder reaction, Friedel-Crafts reaction, Nazarov cyclization reaction, Mukaiyama aldol condensation reaction. [20][21][22][23] The Rauhut-Currier (RC) reaction is also an important basic reaction for the efficient construction of carbon-carbon bonds, [24][25][26] and which can be traced back to a US patent by Rauhut, M and Currier, H [27] in 1963. The RC reaction is the formation of a new carbon-carbon bond between the α-position of an unsaturated olefin and the βposition of another unsaturated alkene under the catalysis of a nucleophilic catalyst.…”