Light-Triggered Click Chemistry

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(12), P. 6991 - 7031

Published: Oct. 26, 2020

The merging of click chemistry with discrete photochemical processes has led to the creation a new class reactions, collectively known as photoclick chemistry. These light-triggered reactions allow synthesis diverse organic structures in rapid and precise manner under mild conditions. Because light offers unparalleled spatiotemporal control over generation reactive intermediates, become an indispensable tool for wide range spatially addressable applications including surface functionalization, polymer conjugation cross-linking, biomolecular labeling native cellular environment. Over past decade, growing number have been developed, especially those based on 1,3-dipolar cycloadditions Diels-Alder owing their excellent reaction kinetics, selectivity, biocompatibility. This review summarizes recent advances development chemical biology materials science. A particular emphasis is placed historical contexts mechanistic insights into each selected reactions. in-depth discussion presented here should stimulate further field, design photoactivation modalities, continuous expansion λ-orthogonal tandem chemistry, innovative use these unique tools bioconjugation nanomaterial synthesis.

Language: Английский

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Catalytic Asymmetric (4+3) Cyclizations of In Situ Generated ortho‐Quinone Methides with 2‐Indolylmethanols

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(26), P. 8703 - 8708

Published: April 12, 2019

Abstract The first catalytic asymmetric (4+3) cyclization of in situ generated ortho ‐quinone methides with 2‐indolylmethanols has been established, which constructed seven‐membered heterocycles high yields (up to 95 %) and excellent enantioselectivity 98 %). This approach not only represents the o ‐hydroxybenzyl alcohols, but also enabled an unprecedented 2‐indolylmethanols. In addition, a scarcely reported para methide derivatives was accomplished.

Language: Английский

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Self-healing by Diels-Alder cycloaddition in advanced functional polymers: A review

Progress in Materials Science, Journal Year: 2022, Volume and Issue: 131, P. 101001 - 101001

Published: Aug. 23, 2022

The ability of artificial materials to be healed efficiently, mimicking the living organisms, exhibits a great deal potential advantages that can revolutionise operation and maintenance used in various applications. Such self-healable smart have been extensively researched last few decades, leading development different physical chemical synthesis approaches. Among these methods, techniques based on reversible cycloadditions or disulfide bonding provide obvious terms repeatability, which holds prime importance determining commerciality healing approach. This review compiles recent advances field self-healing polymers where is introduced by cycloaddition reactions while focusing mainly Diels-Alder (DA) reaction. DA [4 + 2] reaction diene dienophile pairs are fabricate thermally crosslinked networks. These covalent bonds necessary reversibility matrix impart desired strength polymeric material. There considerable body literature has employed either its own along with other mechanisms polymers. However, lack systematic discussing works makes it difficult for beginner cope advancements this field. Most early studies focused stimuli efficiency but review, we would like explore thermodynamics governing rupture–repair process use advanced spectroscopic study them their applicability thermosets, epoxy resins, biopolymers, polymer nanocomposites. Novel applications such functional polymers, multifunctional healable outlook future research, opportunities challenges area also discussed.

Language: Английский

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Lactones: Classification, synthesis, biological activities, and industrial applications

Tetrahedron, Journal Year: 2021, Volume and Issue: 84, P. 132001 - 132001

Published: Feb. 15, 2021

Language: Английский

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Progress in organocatalytic asymmetric (4+3) cycloadditions for the enantioselective construction of seven-membered rings

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(4), P. 966 - 992

Published: Feb. 15, 2023

Language: Английский

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Dienes as Versatile Substrates for Transition Metal‐Catalyzed Reactions

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 4, 2024

Abstract Dienes have been of great interest to synthetic chemists as valuable substrates due their abundance and ease synthesis. Their unique stereoelectronic properties enable broad reactivity with a wide range transition metals construct molecular complexity facilitating synthesis biologically active compounds. In addition, structural diene variation can result in substrate‐controlled reactions, providing mechanistic insights into selectivity patterns. The last decade has seen wealth new methodologies involving through the power metal catalysis. This review summarizes recent advances remaining opportunities for metal‐catalyzed transformations dienes.

Language: Английский

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N‐Heterocyclic Carbene Catalyzed Photoenolization/Diels–Alder Reaction of Acid Fluorides

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(8), P. 3190 - 3194

Published: Dec. 9, 2019

Abstract The combination of light activation and N‐heterocyclic carbene (NHC) organocatalysis has enabled the use acid fluorides as substrates in a UVA‐light‐mediated photochemical transformation previously observed only with aromatic aldehydes ketones. Stoichiometric studies TD‐DFT calculations support mechanism involving photoactivation an ortho ‐toluoyl azolium intermediate, which exhibits “ketone‐like” reactivity under UVA irradiation. Using this photo‐NHC catalysis approach, novel photoenolization/Diels–Alder (PEDA) process was developed that leads to diverse isochroman‐1‐one derivatives.

Language: Английский

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Fluorinated Alcohols: Magic Reaction Medium and Promoters for Organic Synthesis

The Chemical Record, Journal Year: 2019, Volume and Issue: 20(2), P. 142 - 161

Published: July 2, 2019

Abstract Fluorinated alcohols have been widely used in the synthetic organic chemistry over past decades. The unique properties such as strong hydrogen‐bonding donor ability and low nucleophilicity allow them to promote reactions absence of any catalyst. These approaches distinct advantages terms operational simplicity, practicability environmental friendliness. Reactions promoted by fluorinated alcohols, including nucleophilic substitution reactions, annulation electrophilic dearomatization functionalization multiple bond, epoxidation miscellaneous summarized this account.

Language: Английский

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Cooperative Catalysis for the Highly Diastereo‐ and Enantioselective [4+3]‐Cycloannulation of ortho‐Quinone Methides and Carbonyl Ylides

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(14), P. 5536 - 5540

Published: Jan. 2, 2020

We describe herein a highly diastereo- and enantioselective [4+3]-cycloannulation of ortho-quinone methides carbonyl ylides to furnish functionalized oxa-bridged dibenzooxacines with excellent yields stereoselectivity in single synthetic step. The combination rhodium chiral phosphoric acid catalysis working concert generate both transient intermediates situ provides direct access complex bicyclic products two quaternary one tertiary stereogenic centers. may be further into valuable enantiomerically enriched building blocks.

Language: Английский

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Highly Regio‐, Diastereo‐, and Enantioselective Synthesis of Tetrahydroazepines and Benzo[b]oxepines through Palladium‐Catalyzed [4+3] Cycloaddition Reactions

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(3), P. 1243 - 1247

Published: Oct. 14, 2019

Abstract A novel Pd 0 ‐catalyzed asymmetric [4+3] annulation reaction of two readily accessible starting materials has been developed for building seven‐membered heterocyclic architectures. The potential [3+2] side pathway could be suppressed though fine tuning the conditions. broad scope cycloaddition donors and acceptors participated in transformation with excellent chemo‐, regio‐, diastereo‐, enantioselectivtities, leading to valuable tetrahydroazepines benzo[ b ]oxepines.

Language: Английский

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