Chalcogen bonding catalysis

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(2), P. 586 - 605

Published: Dec. 7, 2023

Catalysts play a major role in chemical synthesis, and catalysis is considered to be green economic process. Catalysis dominated by covalent interactions between the catalyst substrate. The design of non-covalent catalysts came into limelight only recently. Hydrogen bonding (HB) are well established among catalysts, including asymmetric HB catalysts. Though halogen (XB) its version gaining admiration, chalcogen (ChB) budding stage. This tutorial review will focus on recently evolved emphasis given chiral molecules. Since successful enantioselective yet reported, this basics catalysis, chalcogenide rigidification transition states ChB, stabilization cations chalcogens, details unsuccessful enantioseparation racemic molecules using existence ChB biomolecules.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(35)

Published: May 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.

Language: Английский

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Halogen Bond Catalysis: A Physical Chemistry Perspective

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(3), P. 507 - 527

Published: Jan. 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.

Language: Английский

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Chiral Hypervalent Bromine(III) (Bromonium Salt): Hydrogen- and Halogen-Bonding Bifunctional Asymmetric Catalysis by Diaryl-λ³-bromanes

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

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Tuning the Halogen Bonding Strength of Cyclic Diaryliodonium Salts

Helvetica Chimica Acta, Journal Year: 2021, Volume and Issue: 104(2)

Published: Jan. 8, 2021

Abstract Diaryliodonium(III) salts have recently received increasing interest as a new class of strong halogen bonding noncovalent organocatalysts. Even though this utilization their Lewis acidity has only been investigated in few studies, high potential comparison to classical monovalent iodine based XB donors become very apparent. So far, acyclic and cyclic five‐membered core structures used, titration studies shown the latter be superior terms binding constants towards bases. Herein, we now compare activity these iodolium with those six‐membered iodininium derivatives. X‐Ray structural analyses, ITC measurements reaction kinetics Ritter ‐type solvolysis wet acetonitrile (a typical bond donor benchmark reaction) all demonstrate that are stronger catalysts than salts. Subsequently, were able improve both significantly by introducing electron‐withdrawing substituents.

Language: Английский

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Zwitterionic iodonium species afford halogen bond-based porous organic frameworks

Chemical Science, Journal Year: 2022, Volume and Issue: 13(19), P. 5650 - 5658

Published: Jan. 1, 2022

Porous architectures characterized by parallel channels arranged in honeycomb or rectangular patterns are identified two polymorphic crystals of a zwitterionic 4-(aryliodonio)-benzenesulfonate. The filled with disordered water molecules which can be reversibly removed on heating. Consistent the remarkable strength and directionality halogen bonds (XBs) driving crystal packing formation, porous structure is stable fully preserved almost quantitative removal readsorption water. systems described here first reported cases one-component 3D organic frameworks whose assembly driven XB only (XOFs). These proof concept for ability aryliodonium tectons affording robust XOFs. high XBs formed these zwitterions geometrical constraints resulting from tendency their hypervalent iodine atoms to act as bidentate donors might key factors determining this ability.

Language: Английский

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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

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

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A Bidentate Antimony Pnictogen Bonding Host System

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Sept. 29, 2023

Abstract A bidentate pnictogen bonding host‐system based on 1,8‐diethynylanthracene was synthesized by a selective tin‐antimony exchange reaction and investigated regarding its ability to act as Lewis acidic host component for the complexation of basic or anionic guests. In this work, novel C≡C−Sb(C 2 F 5 ) unit established study potential antimony(III) sites representatives scarcely explored donors. The capability partly fluorinated system towards halide anions (Cl − , Br I ), dimethyl chalcogenides Me Y (Y=O, S, Se, Te), nitrogen heterocycles (pyridine, pyrimidine). Insights into adduct formation behavior well situation such E⋅⋅⋅Sb−C moieties were obtained in solution means NMR spectroscopy, solid state X‐ray diffraction, elemental analyses, computational methods (DFT, QTAIM, IQA), respectively.

Language: Английский

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Cyclic Diaryliodonium Salts: Eco‐Friendly and Versatile Building Blocks for Organic Synthesis

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(8), P. 1112 - 1139

Published: Feb. 28, 2023

Abstract Cyclic diaryliodoniums are an important class of high‐valent aromatic iodine reagents for the synthesis various axially chiral biaryls and biaryl compounds. Moreover, transition‐metal‐catalyzed annulation has been established construction heterocyclic rings ladder‐type π‐conjugated polycyclic hydrocarbons with readily available cyclic as starting materials. As halogen‐bonding donors, aryliodoniums have explored organocatalysts in a variety organic reactions. In this review, application progress systematically outlined, which highlights recent developments reactions diaryliodoniums, including synthetic application, limitations reaction mechanisms representative cascade to provide insights development prospects diaryliodoniums. magnified image

Language: Английский

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Solvent-modulated binding selectivity of reaction substrates to onium-based σ-hole donors

Catalysis Science & Technology, Journal Year: 2023, Volume and Issue: 13(11), P. 3375 - 3385

Published: Jan. 1, 2023

Solvation effects might play the dominant role in catalysis providing an increase or suppression of activity organocatalysts.

Language: Английский

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