Influence of Coordination to Silver(I) Centers on the Activity of Heterocyclic Iodonium Salts Serving as Halogen‐Bond‐Donating Catalysts DOI
Mikhail V. Il’in, Denis A. Polonnikov, Alexander S. Novikov

et al.

ChemPlusChem, Journal Year: 2023, Volume and Issue: 88(10)

Published: Sept. 7, 2023

Kinetic data based on 1 H NMR monitoring and computational studies indicate that in solution, pyrazole-containing iodonium triflates silver(I) triflate bind to each other, such an interplay results the decrease of total catalytic activity mixture these Lewis acids compared separate catalysis Schiff condensation, imine-isocyanide coupling, or nucleophilic attack a triple carbon-carbon bond. Moreover, kinetic cooperation with prevention decomposition salts during reaction progress. XRD study confirms coordinates center via pyrazole N atom produce rare example pentacoordinated trigonal bipyramidal dinuclear complex featuring cationic ligands.

Language: Английский

Recent Progress in Cyclic Aryliodonium Chemistry: Syntheses and Applications DOI Creative Commons
Xiaopeng Peng, Abdur Rahim, Weijie Peng

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(4), P. 1364 - 1416

Published: Jan. 17, 2023

Hypervalent aryliodoumiums are intensively investigated as arylating agents. They excellent surrogates to aryl halides, and moreover they exhibit better reactivity, which allows the corresponding arylation reactions be performed under mild conditions. In past decades, acyclic aryliodoniums widely explored However, unmet need for is improvement of their notoriously low reaction economy because coproduced iodides during often wasted. Cyclic have intrinsic advantage in terms economy, started receive considerable attention due valuable synthetic applications initiate cascade reactions, can enable construction complex structures, including polycycles with potential pharmaceutical functional properties. Here, we summarizing recent advances made research field cyclic aryliodoniums, nascent design aryliodonium species applications. First, general preparation typical diphenyl iodoniums described, followed by heterocyclic monoaryl iodoniums. Then, initiated arylations coupled subsequent domino summarized construct polycycles. Meanwhile, building biaryls axial atropisomers discussed a systematic manner. Finally, very advance employed halogen-bonding organocatalysts described.

Language: Английский

Citations

71
Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents DOI Creative Commons
Akira Yoshimura, Viktor V. Zhdankin

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Language: Английский

Citations

28
Zwitterionic Dual Halogen Bond-Catalyzed Electrophilic Bromination of Electron-Deficient Arenes under Mild Conditions DOI
Muyin Zhang, Zhihai Ke

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4270 - 4279

Published: Feb. 25, 2025

Language: Английский

Citations

2
Diaryliodoniums as Hybrid Hydrogen- and Halogen-Bond-Donating Organocatalysts for the Groebke–Blackburn–Bienaymé Reaction DOI Creative Commons
Mikhail V. Il’in, Alexandra A. Sysoeva, Alexander S. Novikov

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(7), P. 4569 - 4579

Published: Feb. 17, 2022

Dibenziodolium and diphenyliodonium triflates display high catalytic activity for the multicomponent reaction that leads to a series of imidazopyridines. Density functional theory (DFT) calculations indicate both salts can play role hybrid hydrogen- halogen-bond-donating organocatalysts, which electrophilically activate carbonyl imine groups during process. The ortho-H atoms in vicinal position I atom dual role: forming additional noncovalent bonds with ligated substrate increasing maximum electrostatic potential on σ-hole at iodine owing effects polarization. triflate exhibits higher activity, results obtained from 1H nuclear magnetic resonance (NMR) titrations, conjunction those DFT calculations, this could be explained terms energy required rotation phenyl ring cation ligation substrate.

Language: Английский

Citations

55
Sulfonium and Selenonium Salts as Noncovalent Organocatalysts for the Multicomponent Groebke–Blackburn–Bienaymé Reaction DOI
Mikhail V. Il’in, Alexander S. Novikov, Dmitrii S. Bolotin

et al.

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(15), P. 10199 - 10207

Published: July 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.

Language: Английский

Citations

40
Chiral Hypervalent Bromine(III) (Bromonium Salt): Hydrogen- and Halogen-Bonding Bifunctional Asymmetric Catalysis by Diaryl-λ3-bromanes DOI
Yasushi Yoshida, Takashi Mino, Masami Sakamoto

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(21), P. 13028 - 13033

Published: Oct. 13, 2021

Bromonium salts, which are hypervalent bromine reagents, have been explored as being strong electrophiles owing to their extremely high nucleofugalities. Only one example of catalytic application has reported by our group; however, chiral versions not yet researched. Halogen-bonding (XB) widely applied in chemistry; its successful highly enantioselective Lewis acid catalysis achieved. Herein, we report the design and development cyclic diarylbromonium salts. These catalysts enabled a XB catalysis, giving products with up 96% ee.

Language: Английский

Citations

49
Carbonyl Hypoiodites as Extremely Strong Halogen Bond Donors DOI Creative Commons
Shilin Yu, Jas S. Ward, Khai‐Nghi Truong

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(38), P. 20739 - 20743

Published: July 16, 2021

Abstract Neutral halogen‐bonded O−I−N complexes were prepared from in situ formed carbonyl hypoiodites and aromatic organic bases. The have a strongly polarized iodine atom with larger σ‐holes than any known uncharged halogen bond donor. Modulating the Lewis basicity of selected pyridine derivatives carboxylates leads to where classical O−I⋅⋅⋅N transforms more into COO − ⋅⋅⋅I−N + ion‐pair (salt) an asymmetric moiety. X‐ray analyses, NMR studies, calculations reveal bonding geometries hypoiodite‐based complexes, confirming that solid‐state is much closer N‐atom its original position at carboxylate O‐atom.

Language: Английский

Citations

43
Chiral Binaphthyl‐Based Iodonium Salt (Hypervalent Iodine(III)) as Hydrogen‐ and Halogen‐Bonding Bifunctional Catalyst: Insight into Abnormal Counteranion Effect and Asymmetric Synthesis of N,S‐Acetals DOI
Yasushi Yoshida,

Tappei Fujimura,

Takashi Mino

et al.

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(6), P. 1091 - 1098

Published: Jan. 19, 2022

Abstract Asymmetric construction of chiral N , S ‐acetal skeletons is important because they are widely present in natural products and pharmaceuticals. Halogen‐bonding a unique interaction that has been an organic synthesis focus, although research into variants limited. Halonium salts have found to act as halogen‐bonding catalysts asymmetric catalysis using bromonium under basic conditions was recently discovered by our group. Herein, we report the syntheses ‐acetals good‐to‐excellent yields enantioselectivities (82–97% ee) through bulky thiol additions imines catalysed iodonium salt neutral conditions. The reaction mechanism studied NMR experiments DFT calculations plausible intermediate, which revealed imine substrate activated catalyst bidentate manner. abnormal counteranion effect observed for tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate anion system examined 1 H spectroscopy. magnified image

Language: Английский

Citations

33
The synergism of sequential paired electrosynthesis with halogen bonding activation for the cyclization of organochlorides with olefins DOI

Fei Lian,

Kun Xu, Cheng‐Chu Zeng

et al.

Science China Chemistry, Journal Year: 2022, Volume and Issue: 66(2), P. 540 - 547

Published: Dec. 14, 2022

Language: Английский

Citations

32
Electrochemical Atom Transfer Radical Addition of Polychloroalkanes to Olefins Promoted by 4,4‐Di‐tert‐butyl Bipyridine DOI

Fei Lian,

Fei‐Xian Luo, Meng Wang

et al.

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(13), P. 1583 - 1588

Published: Feb. 14, 2023

Comprehensive Summary A new electrochemical strategy for the atom transfer radical addition (ATRA) of polychloroalkanes across olefins has been realized by synergism paired electrolysis and halogen bonding activation. Notably, readily accessible 4,4‐di‐ tert ‐butyl bipyridine (dtbpy), acting as a acceptor, shifted reduction potential C—Cl bonds positively 110 mV. The decreased operating leads to wide substrate scope excellent functional group compatibility. diverse array terminal internal alkenes such (hetero)aryl olefins, unactive aliphatic natural products drugs‐derived were well compatible.

Language: Английский

Citations

21