On the Question of Zwitterionic Intermediates in the [3+2] Cycloaddition Reactions: A Critical Review
Organics · pp. 49–69 · Published 26 Nov 2020
10.3390/org1010005Abstract
New discoveries require a fundamental revision of the view on the mechanism of the 32CAreaction (according to the older nomenclature defined as 1,3-dipolar cycloaddition reactions). The view of the one-step, “concerted” mechanism of such processes developed in the 20-century is very popular today, both in academic literature and among organic chemists who do not specialize in such transformations. Meanwhile, more and more reports bring examples of reactions that clearly cannot be treated as processes without intermediates. However, these examples are documented very differently. In addition to comprehensive studies using many complementary research techniques, there are also reports in which the presence of intermediates in the cycloaddition environment is postulated on the basis of very unreliable premises. This review is an attempt at a critical analysis and systematization of data in the presented area.
References (68)
- 1 Buchner, 1888, Einwirkung von Diazoessigäther auf die Aether ungesättigter Säuren [DOI]
- 2 Huisgen, 1963, Kinetics and Mechanism of 1,3-Dipolar Cycloadditions [DOI]
- 3 Huisgen, 1976, 1,3-Dipolar cycloadditions. 76. Concerted nature of 1,3-dipolar cycloadditions and the question of diradical intermediates [DOI]
- 4 Hoffman, R.V. (2004). Organic Chemistry, Wiley. [2nd ed.]. [DOI]
- 5 Carey, F.A., and Sundberg, R.J. (2007). Advanced Organic Chemistry. Part A: Structure and Mechanisms, Springer. [5th ed.].
- 6 Huisgen, 1968, Cycloadditions—Definition, Classification, and Characterization [DOI]
- 7 Huisgen, 1980, Cycloaddition mechanism and the solvent dependence of rate [DOI]
- 8 Firestone, 1968, Mechanism of 1,3-dipolar cycloadditions [DOI]
- 9 Firestone, R.A. (1970). Applications of the Linnett electronic theory to organic chemistry. Part III. Linnett structures for 1,3-dipoles and for the diradical intermediates in 1,3-dipolar cycloadditions. J. Chem. Soc. A., 1570–1575. [DOI]
- 10 Firestone, 1972, Application of the Linnett electronic theory to organic chemistry. V. Orientation in 1,3-dipolar cycloadditions according to the diradical mechanism. Partial formal charges in the Linnett structures of the diradical intermediate [DOI]
- 11 Huisgen, 1986, The first two-step 1,3-dipolar cycloadditions: Interception of intermediate [DOI]
- 12 Huisgen, 1986, The first two-step 1,3-dipolar cycloadditions: Non-stereospecificity [DOI]
- 13 Domingo, L.R. (2016). Molecular Electron Density Theory: A Modern View of Reactivity in Organic Chemistry. Molecules, 21. [DOI]
- 14 Domingo, 2019, Unravelling the Mysteries of the 32CAReactions [DOI]
- 15 Domingo, 2009, Understanding the mechanism of polar Diels—Alder reactions [DOI]
- 16 Fialkov, Y.Y. (1990). Rastvoritel’ kak Sredstvo Upravlenia Khimicheskim Processom, Khimya.
- 17 Schwetlick, K. (1971). Kinetische Metoden zur Untersuchung von Reaktionsmechanismen, VEB Deutscher Verlag der Wissenschaften.
- 18 Lan, 2010, Mechanism and Stereoselectivity of the Stepwise 1,3-Dipolar Cycloadditions between a Thiocarbonyl Ylide and Electron-Deficient Dipolarophiles: A Computational Investigation [DOI]
- 19 Domingo, 2004, A DFT study of the Huisgen 1,3-dipolar cycloaddition between hindered thiocarbonyl ylides and tetracyanoethylene [DOI]
- 20 Huisgen, 2005, 2,2,6,6-Tetramethylcyclohexanethione S-methylide, a highly hindered thiocarbonyl ylide: Two-step cycloadditions [DOI]
- 21 Huisgen, 2002, Cycloadditions of two thiocarbonyl ylides with α,β-unsaturated esters and nitriles: Steric course and mechanism [DOI]
- 22 Mloston, 2002, Reactions of a sterically hindered tetrasubstituted thiocarbonyl ylide with acceptor-substituted ethylenes; regioselectivity and stereochemistry [DOI]
- 23 Huisgen, 2002, 1,3-dipolar cycloadditions, part 126. Reactions of sterically hindered ’thiocarbonyl ylides’ with 1,2-bis(trifluoromethyl)ethene-1,2-dicarbonitrile: Isolation of a cyclic seven-membered ketene imine [DOI]
- 24 Huisgen, 2001, Cycloadditions of ’thiocarbonyl ylides’ with tetracyanoethylene (=ethenetetracarbonitrile): Interception of intermediates [DOI]
- 25 Mloston, 1989, 1,3-cycloadditions of aliphatic thione S-methylides to dimethyl 2,3-dicyanofumarate and 2,3-dicyanomaleate; a test case for steric course and mechanism [DOI]
- 26 Huisgen, 1992, Can polymerization trap intermediates in 1,3-dipolar cycloadditions? [DOI]
- 27 2015, In the searching for zwitterionic intermediates on reaction paths of 32CAreactions between 2,2,4,4-tetramethyl-3-thiocyclobutanone S-methylide and polymerizable olefins [DOI]
- 28 2020, A DFT study on the molecular mechanism of the conjugated nitroalkenes polymerization process initiated by selected unsaturated nucleophiles [DOI]
- 29 Baran, 1987, First [4+3]-cycloaddition of a 1,3-dipole with a 1,3-diene [DOI]
- 30 Baran, 1989, Competing [2+3] and [4+3] cycloadditions of C,N-diphenylnitrone with 1,3-dienes. Evidence for thermally nonequilibrated intermediates [DOI]
- 31 Yin, 2018, Application of (4+3) cycloaddition strategies in the synthesis of natural products [DOI]
- 32 2020, A new insight on the molecular mechanism of the reaction between (Z)-C,N-diphenylnitrone and 1,2-bismethylene-3,3,4,4,5,5-hexamethylcyclopentane [DOI]
- 33 Koroniak, 2012, Synthesis of 5-fluorovinyl derivatives of pyrimidines via Suzuki–Miyaura coupling and their 1,3-dipolar cycloaddition reactions with nitrones [DOI]
- 34 Linden, 2006, Reactions of 2-Unsubstituted 1H-Imidazole 3-Oxides with 2,2-Bis(trifluoromethyl)ethene-1,1-dicarbonitrile: A Stepwise 1,3-Dipolar Cycloaddition [DOI]
- 35 2018, β-Trifluoromethylated nitroethenes in Diels-Alder reaction with cyclopentadiene: A DFT computational study [DOI]
- 36 2018, Competition between one-step and two-step mechanism in polar [3+2] cycloadditions of (Z)-C-(3,4,5-trimethoxyphenyl)-N-methyl-nitrone with (Z)-2-EWG-1-bromo-1-nitroethenes [DOI]
- 37 Dresler, 2016, [3+2] Cycloadditions of 1-halo-1-nitroethenes with (Z)-C-(3,4,5-trimethoxyphenyl)-N-methyl-nitrone as regio- and stereocontrolled source of novel bioactive compounds: Preliminary studies
- 38 Demchuk, 2014, Regio- and stereoselectivity of polar [2+3] cycloaddition reactions between (Z)-C-(3,4,5-trimethoxyphenyl)-N-methylnitrone and selected (E)-2-substituted nitroethenes
- 39 2009, Regio- and stereoselectivity of [2+3]cycloaddition of nitroethene to (Z)-N-aryl-C-phenylnitrones [DOI]
- 40 2020, Selenyl analog of the (Z)-C,N-diphenylnitrone as the TAC in [3+2] cycloaddition with nitroethene: A DFT computational study [DOI]
- 41 Kula, 2018, A DFT computational study on the [3+2] cycloaddition between parent thionitrone and nitroethene [DOI]
- 42 2015, A stepwise, zwitterionic mechanism for the 1,3-dipolar cycloaddition between (Z)-C-4-methoxyphenyl-N-phenylnitrone and gem-chloronitroethene catalysed by 1-butyl-3-methylimidazolium ionic liquid cations [DOI]
- 43 2016, First example of stepwise, zwitterionic mechanism for bicyclo[2.2.1]hept-5-ene (norbornene) formation process catalyzed by the 1-butyl-3-methylimidazolium cations [DOI]
- 44 2013, Competition between the one-step and two-step, zwitterionic mechanisms in the [2+3] cycloaddition of gem-dinitroethene with (Z)-C, N-diphenylnitrone: A DFT computational study [DOI]
- 45 Tartakovskii, 1968, O-мeтиловый зφиp нитpодимeтилмaлонaтa в peaкции 1,3-диполяpноgо циклопpиcоeдинeния
- 46 2020, Push-pull nitronates in the 32CAwith nitroethylene: Molecular Electron Density Theory study [DOI]
- 47 Loska, 2006, Simple method for the introduction of tetrafluoroethyl substituents into nitrogen heterocycles [DOI]
- 48 Jin, 2019, The Carbocation-Catalyzed Intermolecular Formal [2+2+1] Cycloaddition of Ynamides with Quinoxaline N-Oxides [DOI]
- 49 Cramer, C.J. (2002). Essentials of Computational Chemistry. Theories and Models, Wiley.
- 50 Elender, 2000, 1,3-Dipolar Cycloaddition Reactions of Stable Bicyclic and Monocyclic Azomethine Ylides: Kinetic Aspects [DOI]
- 51 Domingo, 2020, Unveiling the Reactivity of Cyclic Azomethine Ylides in 32CAReactions within the Molecular Electron Density Theory [DOI]
- 52 Mloston, 2009, Thermal [2+3]-Cycloadditions of trans-1-Methyl-2,3-diphenylaziridine with C=S and C=C Dipolarophiles: An Unexpected Course with Dimethyl Dicyanofumarate [DOI]
- 53 Dresler, 2017, A unique example of noncatalyzed 32CAinvolving (2E)-3-aryl-2-nitroprop-2-enenitriles [DOI]
- 54 Kula, 2017, Unexpected course of reaction between (E)-2-aryl-1-cyano-1-nitroethenes and diazafluorene: Why is there no 1,3-dipolar cycloaddition? [DOI]
- 55 Beltrame, P., Sartirana, P., and Vintani, C. (1971). Relative rates of the concurrent reactions in the addition of a substituted benzonitrile oxide to arylacetylenes. J. Chem. Soc. B, 814–817. [DOI]
- 56 Dondoni, A., and Barbaro, G. (1974). Kinetics of addition and cycloaddition of phenylacetylene to benzonitrile N-oxides. Competitive concerted and stepwise mechanisms. J. Chem. Soc. Perkin Trans., 1591–1594. [DOI]
- 57 Baran, 1989, Mechanistic impact of oxime formation accompanying 1,3-dipolar cycloadditions of nitrile oxides [DOI]
- 58 2015, Nitroacetylene as dipolarophile in [2+3] cycloaddition reactions with allenyl-type three-atom components: DFT computational study [DOI]
- 59 Siadati, 2015, An example of a stepwise mechanism for the catalyst-free 1,3-dipolar cycloaddition between a nitrile oxide and an electron rich alkene [DOI]
- 60 Siadati, 2016, The Effect of Position Replacement of Functional Groups on the Stepwise character of 1,3-Dipolar Reaction of a Nitrile Oxide and an Alkene [DOI]
- 61 Quast, 1990, Zwitterions as Intermediates of the 1,3-Dipolar Cycloaddition of Electrophilic Azides to 5-Alkylidenedihydrotetrazoles-the Other Non-Concerted Limiting Case [DOI]
- 62 Quast, 1996, Zwitterions as Intermediates in 1,3-Dipolar Cycloadditions of Electrophilic Azides to 2-Alkylidenetetrahydroimidazoles and 2-Alkylidenedihydrobenzimidazoles [DOI]
- 63 Shimizu, 1978, Cycloaddition of Diazoalkanes to Penta- and Hexafluoroacetones. Isolation of A 3 -1,3,4-Oxadiazolines and Their Decomposition via Carbonyl Ylides [DOI]
- 64 2015, On the question of zwitterionic intermediates in 1,3-dipolar cycloadditions between hexafluoroacetone and sterically crowded diazocompounds [DOI]
- 65 Celeda, 2019, Experimental and Computational Studies on Stepwise [3+2]-Cycloadditions of Diaryldiazomethanes with Electron-Deficient Dimethyl (E)- and (Z)-2,3-Butenedioates [DOI]
- 66 Kula, 2020, A DFT Study on the Barton–Kellogg Reaction—The Molecular Mechanism of the Formation of Thiiranes in the Reaction between Diphenyldiazomethane and Diaryl Thioketones [DOI]
- 67 Huisgen, 2006, 1,3-Dipolar cycloadditions of diphenyldiazomethane to thioketones: Rate measurements disclose thiones to be superdipolarophiles [DOI]
- 68 Urbaniak, 2016, New Applications of Hetaryl Thioketones for the Synthesis of Hetaryl-Substituted Ethenes via ’Two-Fold Extrusion Reaction [DOI]
Cited by 151
Shuming Chen, Tuo Hu, Kendall N. Houk · The Journal of Organic Chemistry · 2021
Grzegorz Mlostoń, Karolina Kula, Radomir Jasiński · Molecules · 2021
Seyyed Amir Siadati, Akbar Dadras, Mohammad Amin Rezvanfar · Combinatorial Chemistry & High Throughput Screening · 2021
Le Li, Robert J. Mayer, David S. Stephenson · Chemistry - A European Journal · 2022
Eugene V. Babaev, Ivan A. Shadrin · Molecules · 2021
Ekaterina E. Khramtsova, Ekaterina A. Lystsova, М. В. Дмитриев · ChemistrySelect · 2021
Barbara Gawdzik, Joanna Drzeżdżon, Tatsiana Siarhei · Materials · 2021
Radomir Jasiński · Chemistry of Heterocyclic Compounds · 2022
Ewa Dresler · Scientiae Radices · 2024
Sadeq M. Al‐Hazmy, Mohamed Oussama Zouaghi, Nasser Amri · Molecules · 2023
Showing 81 of 151 known citations — external sources report more than can currently be individually listed.
Related research
- A Novel Catalytic Synthesis of Flavones under Autoclave Conditions and Comparative Study of Anti-cancer Activity — shares topic coverage
- Thermostability and in-vitro Antibacterial Activity of Aqueous Extracts of Tetrapleura tetraptera Pods on Multidrug Resistant Clinical Isolates — shares topic coverage
- Acute Toxicity, Phytochemistry and Anti-diarrheal Effects of Celtis integrifolia Lam. Aqueous Leaf Extract in Wistar Albino Rats — shares topic coverage
- Understanding the Reactivity of Trimethylsilyldiazoalkanes Participating in [3+2] Cycloaddition Reactions towards Diethylfumarate with a Molecular Electron Density Theory Perspective — shares topic coverage
- Understanding the Origin of the Regioselectivity in Non-Polar [3+2] Cycloaddition Reactions through the Molecular Electron Density Theory — shares topic coverage
Article metrics
Real usage data collected on this platform.
0
Page views
0
PDF downloads
0
Outbound clicks
151
Citations
Views by country
Approximate, from request IP at view time — not citizenship or institution. Countries with fewer than 5 views are grouped as "Other".
No views recorded yet.
Traffic sources
Referring site, by host.
No traffic recorded yet.
Views and downloads exclude known bots/crawlers. Citations combines this platform's own DOI-resolved index with each external source's own reported total — see Cited by above for individually listed citing works. Last refreshed 0 seconds ago.