Recognition in the Domain of Molecular Chirality: From Noncovalent Interactions to Separation of Enantiomers

Chemical Reviews, Год журнала: 2022, Номер 122(16), С. 13235 - 13400

Опубликована: Авг. 2, 2022

It is not a coincidence that both chirality and noncovalent interactions are ubiquitous in nature synthetic molecular systems. Noncovalent interactivity between chiral molecules underlies enantioselective recognition as fundamental phenomenon regulating life human activities. Thus, represent the narrative thread of fascinating story which goes across several disciplines medical, chemical, physical, biological, other natural sciences. This review has been conceived with awareness modern attitude toward its consequences needs to be founded on multidisciplinary approaches disclose basis essential phenomena domain With primary aim discussing this topic an integrated way, comprehensive pool rational systematic information provided, concerns fundamentals chirality, description interactions, their implications processes occurring different contexts. A specific focus devoted enantioselection chromatography electromigration techniques because unique feature "multistep" processes. second motivation for writing make clear statement about state art, tools we have at our disposal, what still missing fully understand mechanisms underlying recognition.

Язык: Английский

---

Halogen, Chalcogen, Pnictogen, and Tetrel Bonding in Non‐Covalent Organocatalysis: An Update

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(31)

Опубликована: Май 11, 2024

The use of noncovalent interactions based on electrophilic halogen, chalcogen, pnictogen, or tetrel centers in organocatalysis has gained noticeable attention. Herein, we provide an overview the most important developments last years with a clear focus experimental studies and catalysts which act via such non-transient interactions.

Язык: Английский

---

Three-component enantioselective alkenylation of organophosphonates via nickel metallaphotoredox catalysis

Chem, Год журнала: 2022, Номер 9(1), С. 154 - 169

Опубликована: Окт. 14, 2022

Язык: Английский

---

Sulfonium and Selenonium Salts as Noncovalent Organocatalysts for the Multicomponent Groebke–Blackburn–Bienaymé Reaction

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(15), С. 10199 - 10207

Опубликована: Июль 20, 2022

Sulfonium and selenonium salts, represented by S-aryl dibenzothiophenium Se-aryl dibenzoselenophenium triflates, were found to exhibit remarkable catalytic activity in the model Groebke–Blackburn–Bienaymé reaction. Kinetic analysis density functional theory (DFT) calculations indicated that their effect is induced ligation of reaction substrates σ-holes on S or Se atom cations. The experimental data although 10-fold excess chloride totally inhibits sulfonium salt remains catalytically active, which can be explained experimentally lower binding constant derivative comparison with analogue. Both types salts than dibenziodolium species.

Язык: Английский

---

Fine‐Tuning Substrate–Catalyst Halogen–Halogen Interactions for Boosting Enantioselectivity in Halogen‐Bonding Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(35)

Опубликована: Май 25, 2023

A new approach towards highly enantioselective halogen-bonding catalysis has been developed. To circumvent the intrinsic issues of nature halogen-bond (XB) and resultant unresolved limitations in asymmetric catalysis, fine-tuned halogen-halogen interactions between substrate XB-donor were designed to preorganize catalyst's cavity boost enantiocontrol. The present strategy exploits both electron cloud (Lewis base site) sigma (σ)-hole site halogen substituent substrates form a tight catalyst-substrate-counteranion chiral complex, thus enabling controlled induction high levels chirality transfer. Remarkable enantioselectivities up 95 : 5 e.r. (90 % ee) have achieved model dearomatization reaction halogen-substituted (iso)quinolines with tetrakis-iodotriazole multidentate anion-binding catalysts.

Язык: Английский

---

Halogen Bond Catalysis: A Physical Chemistry Perspective

The Journal of Physical Chemistry A, Год журнала: 2024, Номер 128(3), С. 507 - 527

Опубликована: Янв. 12, 2024

As important noncovalent interactions, halogen bonds have been widely used in material science, supramolecular chemistry, medicinal organocatalysis, and other fields. In the past 15 years, bond catalysis has become a developed field organocatalysis for catalysts' advantages of being environmentally friendly, inexpensive, recyclable. Halogen can induce various organic reactions, powerful alternative to fully explored hydrogen catalysis. From physical chemistry view, this perspective provides an overview latest progress key examples via activation lone pair systems functional group, π systems, metal complexes. The research progresses by our group were also introduced.

Язык: Английский

---

N‐Heterocyclic Iod(az)olium Salts – Potent Halogen‐Bond Donors in Organocatalysis

Chemistry - A European Journal, Год журнала: 2021, Номер 27(52), С. 13128 - 13134

Опубликована: Июнь 23, 2021

This article describes the application of N-heterocyclic iod(az)olium salts (NHISs) as highly reactive organocatalysts. A variety mono- and dicationic NHISs are described utilized potent XB-donors in halogen-bond catalysis. They were benchmarked seven diverse test reactions which activation carbon- metal-chloride bonds well carbonyl nitro groups was achieved. N-methylated rendered highest reactivity all investigated catalytic applications with reactivities even higher than previously monodentate based on iodine(I) (III) strong Lewis acid BF3 .

Язык: Английский

---

Pushing the limits of the hydrogen bond enhanced halogen bond—the case of the C–H hydrogen bond

Chemical Science, Год журнала: 2022, Номер 13(37), С. 11156 - 11162

Опубликована: Янв. 1, 2022

C-H hydrogen bonds have remarkable impacts on various chemical systems. Here we consider the influence of to iodine atoms. Positioning a methyl group between two halogen bond donors receptor engendered intramolecular bonding (HBing) electron-rich belt both donors. When coupled with control molecules, role was evaluated. Gas-phase density functional theory studies indicated that help bias bidentate binding conformation. Interaction energy analysis suggested charged augment interaction-producing >10 kcal mol-1 enhancement over lacking C-H⋯I-C interaction. X-ray crystallographic demonstrated and conformations triflate iodide anions, yet steric bulk central seems impact expected trends in distance. In solution, anion titration data elevated performance from receptors utilize Hydrogen Bond enhanced Halogen Bonds (HBeXBs). Collectively, results suggest even modest acceptors can molecular structure improve performance.

Язык: Английский

---

Application of Thiourea/Halogen Bond Donor Cocatalysis in Metal-Free Cationic Polymerization of Isobutyl Vinyl Ether and Styrene Derivatives

Macromolecules, Год журнала: 2022, Номер 55(13), С. 5756 - 5765

Опубликована: Июнь 27, 2022

Cationic polymerization of isobutyl vinyl ether (IBVE) was investigated using Schreiner's thiourea (STU) combined with Im-TEPB bearing a 2-iodoimidazolium cation and noncoordinating borate anion. Both the CF3CO2H adduct HCl IBVE had ability to initiate polymerization, but number-averaged molecular weight rather low compared theoretical value distribution fairly broad (Mw/Mn > 2.6). On other hand, fast cationic p-methoxystyrene (pMOS, 50 equiv relative pMOS·HCl) proceeded STU/Im-TEPB cocatalysts, giving rise poly(pMOS) Mn = 4580 Mw/Mn 1.38. STU/Im-TfO exhibited decreased activity due coordination trifluoromethanesulfonate counteranion NH group STU, which supported by NMR spectrum, DFT calculation, UV–vis titration experiment. The could be roughly regulated cocatalysis between 2400 7500 monomer feed ratio keeping below 1.41, although these values were lower than ones probably unignorable chain-transfer reaction. kinetics revealed that consumption rate depends on concentration reveals catalytic function STU/Im-TEPB.

Язык: Английский

---

Taming Molecular Folding: Anion-Templated Foldamers with Tunable Quaternary Structures

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(24), С. 16419 - 16427

Опубликована: Июнь 6, 2024

Higher-order foldamers represent a unique class of supramolecules at the forefront molecular design. Herein we control quaternary folding using novel approach that combines halogen bonding (XBing) and hydrogen (HBing). We present first anion-templated double helices induced by bonds (XBs) stabilized "hydrogen bond enhanced bonds" (HBeXBs). Our findings demonstrate number orientation (HB) XB donors significantly affect structure guest selectivity two similar oligomers. This research offers new design elements to engineer tailor their for specific binding.

Язык: Английский

---