Origins of the Reactivity in 1,3‐Dipolar Cycloadditions of Acyl Isocyanide Ylides DOI
Javier Emilio Alfonso Ramos, Ruben Van Lommel, David Hernández‐Castillo

et al.

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 26(3)

Published: Nov. 29, 2022

Abstract 1,3‐Dipolar cycloadditions are the preferred method to generate five‐membered heterocyclic rings. Surprisingly, based on acyl‐isocyanide ylides have remained underexplored by chemical community. Acyl‐isocyanide readily react with dipolarophiles, such as substituted alkenes, yield Δ 1 ‐pyrroline derivatives. As an explanation for observed reactivity of this reaction is lacking, extensive density functional theory calculations were performed scrutinize mechanistic features transformation. Herein we explain experimental outcome using a variety theories and predict opposed regioselectivity electron‐poor electron‐rich dipolarophiles. With insights obtained, hope incentivize design new cycloaddition reactions motif.

Language: Английский

Synthesis of Multisubstituted 1,2,3-Triazoles: Regioselective Formation and Reaction Mechanism DOI Creative Commons

Tzu-Ching Chi,

Po‐Chun Yang,

Shao-Kang Hung

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(8), P. 5401 - 5408

Published: March 28, 2024

A synthetically useful approach to functionalized triazoles is described via the reaction of β-carbonyl phosphonates and azides. 1,4- 1,5-disubstituted 1,4,5-trisubstituted can be regio- chemoselectively accessed under mild conditions in good excellent yields (31 examples, up 99%). mechanism proposed that rationalizes avoidance 4-phosphonate byproducts, which aligned with crystallographic experimental evidence.

Language: Английский

Citations

8
The 1,3‐Dipolar Cycloaddition: From Conception to Quantum Chemical Design DOI Creative Commons
Steven E. Beutick, Pascal Vermeeren, Trevor A. Hamlin

et al.

Chemistry - An Asian Journal, Journal Year: 2022, Volume and Issue: 17(17)

Published: July 13, 2022

The 1,3-dipolar cycloaddition (1,3-DCA) reaction, conceptualized by Rolf Huisgen in 1960, has proven immensely useful organic, material, and biological chemistry. uncatalyzed, thermal transformation is generally sluggish unselective, but the reactivity can be enhanced means of metal catalysis or introduction either predistortion electronic tuning dipolarophile. These promoted reactions go with a much higher reactivity, selectivity, yields, often at ambient temperatures. rapid orthogonal compatibility aqueous physiological conditions positions 1,3-DCA as an excellent bioorthogonal reaction. Quantum chemical calculations have been critical for providing understanding physical factors that control selectivity 1,3-DCAs. In silico derived design principles invaluable new dipolarophiles tailored reactivity. This review discusses everything from conception all way to state-of-the-art methods models used quantum novel (bioorthogonal) reagents.

Language: Английский

Citations

23
Cu-catalyzed cycloaddition of aryl azides to 1-iodobuta-1,3-diynes: an experimental and quantum chemical study of unusual regiochemistry DOI
Anastasia I. Govdi, Natalia A. Danilkina, Andrey A. Shtyrov

et al.

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(11), P. 4831 - 4845

Published: Jan. 1, 2024

The nontrivial CuAAC regiochemistry of aryl azides and 1-iodobutadiynes helped to establish the binuclear character mechanism for iodoalkynes.

Language: Английский

Citations

5
Nitrile Oxide, Alkenes, Dipolar Cycloaddition, Isomerization and Metathesis Involved in the Syntheses of 2-Isoxazolines DOI Creative Commons
Stanisław Krompiec, Piotr Lodowski, Aneta Kurpanik

et al.

Molecules, Journal Year: 2023, Volume and Issue: 28(6), P. 2547 - 2547

Published: March 10, 2023

The involvement of 1,3-dipolar cycloaddition (1,3-DP), double bond migration, metathesis, and nitrile oxide (including in situ-generated oxide) as dipoles, together with the C=C containing dipolarophiles, syntheses 2-isoxazolines is presented. Methods for synthesizing isoxazolines (other than 1,3-DP cycloaddition) were also presented briefly. Various methods preparation, especially procedures, are Special attention was paid to application various combinations migration (DBM) alkene metathesis (AM) trisubstituted isoxazolines. Allyl compounds type QCH2CH=CH2 (Q = ArO, ArS, Ar, others) play role dipolarophile precursors DPC mentioned, DBM AM. Mechanistic aspects cycloadditions, i.e., concerted or stepwise reaction mechanism their regio- stereoselectivity discussed from experimental theoretical points view. Side reactions accompanying cycloaddition, dimerization, considered. 2-Isoxazoline applications organic synthesis biological activity, broad utility medicine, agriculture, other fields raised. Some remaining challenges field finally discussed.

Language: Английский

Citations

12
Recent Developments in the Ruthenium‐Catalyzed Azide Alkyne Cycloaddition (RuAAC) Reaction DOI Creative Commons

Flavia Ferrara,

Tamás Beke‐Somfai, Nina Kann

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(25)

Published: May 10, 2024

Abstract The ruthenium‐catalyzed azide‐alkyne cycloaddition (RuAAC) gives access to 1,5‐disubstitued triazoles in a single atom‐economical step and offers advantages compared its copper‐catalyzed counterpart that both terminal internal alkynes can be employed. This review summarizes recent findings this field during the last eight years, covering mechanistic investigations, synthetic developments, as well applications medicinal chemistry, polymer synthesis physical organic chemistry.

Language: Английский

Citations

4
The literature of heterocyclic chemistry, part XXII, 2022 DOI
Галина А. Газиева, Yu. B. Evdokimenkova, N. O. Soboleva

et al.

Advances in heterocyclic chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

Citations

0
Combining Distibene, Diazoolefins, and Visible Light: Synthesis and Reactivity of Inorganic Rings DOI
Prasenjit Palui,

Sangita Ghosh,

Rosa M. Gomila

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

The chemistry of heterocycles containing "diaza" units has been extensively studied due to their applications ranging from pharmaceuticals advanced materials. In contrast, incorporating heavier elements, such as Sb and Bi, remain exceedingly rare lack straightforward synthetic methodologies. Herein, we present a comprehensive experimental theoretical investigation the first diazadistiboylidenes (1a, 1b), synthesized via [3 + 2]-cycloaddition between distibene diazoolefins. These stiboylidenes are key intermediates promote selective nucleophilic substitution, leading example diantimonyl anion. Furthermore, upon visible-light irradiation, could isolate methylenedistibiranes, analogs methylenediaziridine (C2H4N2). findings offer novel platform for heavy dipnictogen chemistry, showcasing that diazoolefins, in combination with visible light, can facilitate formation unprecedented serve CO2 activation.

Language: Английский

Citations

0
Platinum macrocatalyst for heterogeneous Si–O dehydrocoupling DOI
Konstantin V. Deriabin, Ekaterina A. Golovenko, Nikita S. Antonov

et al.

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(18), P. 5854 - 5858

Published: Jan. 1, 2023

A platinum polymer catalyst (Pt-PDMS) was synthesized by immobilization of a catalytic complex in polysiloxane chain using an azide-alkyne CuAAC cycloaddition. Insoluble Pt-PDMS can be used as effective heterogeneous macrocatalyst for Si-O dehydrocoupling. is easy to recover, purify, and reuse again catalysis.

Language: Английский

Citations

7
[4+1] cyclization of α-diazo esters and mesoionic N-heterocyclic olefins DOI

Qiuming Liang,

Yimin Zeng,

Pedro A. Mendez Ocampo

et al.

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(32), P. 4770 - 4773

Published: Jan. 1, 2023

Prompted by the recent stepwise mechanistic proposal for Huisgen [3+2] cycloaddition reaction between enamine and α-diazo ester, where nucleophilic addition of carbon onto terminal nitrogen diazo ester is crucial, we examined possible use N-heterocyclic olefins (NHOs) as highly electron-rich dipolarophiles in these reactions. The mesoionic NHOs derived from 1,2,3-triazoles undergo fast [4+1] to give 3-(triazolium-4-yl)-(3H)-pyrazol-4-olates at room temperature. mechanism has been explored through experimental DFT computational studies.

Language: Английский

Citations

6
Engaging Isatins and Amino Acids in Multicomponent One-Pot 1,3-Dipolar Cycloaddition Reactions—Easy Access to Structural Diversity DOI Creative Commons
Hua Zhao, Yufen Zhao

Molecules, Journal Year: 2023, Volume and Issue: 28(18), P. 6488 - 6488

Published: Sept. 7, 2023

Multicomponent reactions (MCRs) have undoubtedly emerged as the most indispensable tool for organic chemists worldwide, finding extensive utility in synthesis of intricate natural products, heterocyclic molecules with significant bioactivity, and pharmaceutical agents. The multicomponent one-pot 1,3-dipolar cycloaddition reactions, which were initially conceptualized by Rolf Huisgen 1960, find application contemporary chemistry. In terms green synthesis, is highly favored owing to its numerous advantages, including high step- atom-economies, remarkable product diversity, well excellent efficiency diastereoselectivity. Among pieces research, fascinating reaction involves utilization azomethine ylides generated from isatins amino acids that can be captured various dipolarophiles. This approach offers a efficient convenient method constructing spiro-pyrrolidine oxindole scaffolds, are crucial building blocks biologically active molecules. Consequently, this review delves deeper into dipolarophiles utilized over past six years.

Language: Английский

Citations

6