238:. Isotope exchange studies indicate that for aryl fluorides and, sometimes, aryl chlorides, the elimination event proceeds in two steps, deprotonation, followed by expulsion of the nucleophile. Thus, the process is formally analogous to the E1cb mechanism of aliphatic compounds. Aryl bromides and iodides, on the other hand, generally appear to undergo elimination by a concerted syn-coplanar E2 mechanism. The resulting benzyne forms addition products, usually by nucleophilic addition and protonation. Generation of the benzyne intermediate is the slow step in the reaction.
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Meta substituent can afford both regioisomers as described above. Nucleophilic additions can occur with regioselectivity. Although classic explanations to explain regioselectivity refer to carbanion stability following attack by the nucleophile, this explanation has been replaced by the aryne distortion model by
633:
Multicomponent reactions of arynes are powerful transformations that allow for rapid formation of 1,2-disubstituted arenes. Despite their potential utility, examples of multicomponent aryne reactions in natural product synthesis are scarce. A four-component aryne coupling reaction was employed in the
292:
There are two possible regioisomers of benzyne with substituent (Y): triple bond can be positioned between C2 and C3 or between C3 and C4. Substituents ortho to the leaving group will lead to the triple bond between C2 and C3. Para Y and LG will lead to regioisomer with triple bond between C3 and C4.
73:
Geometric constraints on the triple bond in benzyne result in diminished overlap of in-plane p-orbitals, and thus weaker triple bond. The vibrational frequency of the triple bond in benzyne was assigned by
Radziszewski to be 1846 cm, indicating a weaker triple bond than in unstrained alkyne with
612:
A variety of natural products have been prepared using arynes as intermediates. Nucleophilic additions to arynes have been widely used in natural product total synthesis. Indeed, nucleophilic additions of arynes are some of the oldest known applications of aryne chemistry. Nucleophilic addition to
498:
Two states were proposed for 1,4-didehydrobenzene: singlet and triplet, with the singlet state lower in energy. Triplet state represents two noninteracting radical centers, and hence should abstract hydrogens at the same rate as phenyl radical. However, singlet state is more stabilized than the
368:
cycloadditions of arynes have been commonly applied to natural product total synthesis. The main limitation of such approach, however, is the need to use constrained dienes, such as furan and cyclopentadiene. In 2009 Buszek and co-workers synthesized herbindole A using aryne -cycloaddition.
382:
Due to significant byproduct formation, aryne chemistry is rarely utilized in natural product total synthesis. Nevertheless, several examples do exist. In 1982, Stevens and co-workers reported a synthesis of taxodione that utilized cycloaddition between an aryne and a ketene acetal.
88:
of aryne lies much lower than the LUMO of unstrained alkynes, which makes it a better energy match for the HOMO of nucleophiles. Hence, benzyne possesses electrophilic character and undergoes reactions with nucleophiles. A detailed MO analysis of benzyne was presented in 1968.
512:
The first evidence for arynes came from the work of
Stoermer and Kahlert. In 1902 they observed that upon treatment of 3-bromobenzofuran with base in ethanol 2-ethoxybenzofuran is formed. Based on this observation they postulated an aryne intermediate.
269:
When leaving group (LG) and substituent (Y) are mutually ortho or para, only one benzyne intermediate is possible. However, when LG is meta to Y, then regiochemical outcomes (A and B) are possible. If Y is electron withdrawing, then
141:
Such reactions require strong base and high temperatures. 1,2-Disubstituted arenes serve as precursors to benzynes under milder conditions. Benzyne is generated by the dehalogenation of 1-bromo-2-fluorobenzene by magnesium.
503:
for hydrogen cleavage, leading to slower hydrogen abstraction. Chen proposed the use of 1,4-didehydrobenzene analogues that have large singlet-triplet energy gaps to enhance selectivity of enediyne drug candidates.
301:. In this model, substituents cause geometric distortion of the ground state structure of the aryne, leading to regioselective reactions, consistent with reactions proceeding through early transition states.
331:
results. In this method, the concerted mechanism of the Diels-Alder reaction between benzyne and furan is shown below. Other benzyne cycloadditions are thought to proceed via a stepwise mechanism.
74:
vibrational frequency of approximately 2150 cm. Nevertheless, benzyne is more like a strained alkyne than a diradical, as seen from the large singlet–triplet gap and alkyne-like reactivity.
226:
Even at low temperatures arynes are extremely reactive. Their reactivity can be classified in three main classes: (1) nucleophilic additions, (2) pericyclic reactions, and (3) bond-insertion.
1783:
Polishchuk, A. L.; Bartlett, K. L.; Friedman, L. A.; Jones, M. Jr (2004). "A p-Benzyne to m-Benzyne
Conversion Through a 1,2-Shift of a Phenyl Group. Completion of the Benzyne Cascade".
623:
The synthesis of the tetracyclic meroterpenoid (+)-liphagal involved an aryne intermediate. Their approach employed an aryne cyclization to close the final ring of the natural product.
248:"Aryne coupling" reactions allow for generation of biphenyl compounds which are valuable in pharmaceutical industry, agriculture and as ligands in many metal-catalyzed transformations.
1813:
Richard R. Jones; Robert G. Bergman (1972). "p-Benzyne. Generation as an intermediate in a thermal isomerization reaction and trapping evidence for the 1,4-benzenediyl structure".
427:
are, respectively, 106, 122, and 138 kcal/mol (444, 510 and 577 kJ/mol). The 1,2- and 1,3- isomers have singlet ground states, whereas for 1,4-didehydrobenzene the gap is smaller.
1841:
Clauberg, H.; Minsek, D. W.; Chen, P. (1992). "Mass and photoelectron spectroscopy of C3H2. .DELTA.Hf of singlet carbenes deviate from additivity by their singlet-triplet gaps".
379:
Benzynes undergo cycloaddition with a wide range of alkenes. Due to electrophilic nature of benzyne, alkenes bearing electron-donating substituents work best for this reaction.
1868:
Blush, J. A.; Clauberg, H.; Kohn, D. W.; Minsek, D. W.; Zhang, X.; Chen, P. (1992). "Photoionization mass and photoelectron spectroscopy of radicals, carbenes, and biradicals".
164:. This method has seen wide applicability and was reviewed in 2021. Fluoride displacement of the trimethylsilyl group induces elimination of triflate and release of benzyne:
1959:
Wittig, G.; Pieper, G.; Fuhrmann, G. (1940). "Über die
Bildung von Diphenyl aus Fluorbenzol und Phenyl-lithium (IV. Mitteil. über Austauschreaktionen mit Phenyl-lithium)".
926:
Hoffmann, R.; Imamura, A.; Hehre, W. J. (1968). "Benzynes, dehydroconjugated molecules, and the interaction of orbitals separated by a number of intervening sigma bonds".
437:
The interconversion of the 1,2-, 1,3- and 1,4-didehydrobenzenes has been studied. A 1,2- to 1,3-didehydrobenzene conversion has been postulated to occur in the
47:. Arynes are examples of didehydroarenes (1,2-didehydroarenes in this case), although 1,3- and 1,4-didehydroarenes are also known. Arynes are examples of
573:
1,3-Didehydroarenes was first demonstrated in the 1990s when it was generated from 1,3-disubstituted benzene derivatives, such as the peroxy ester 1,3-C
309:
Benzyne undergoes rapid dimerization to form biphenylene. Some routes to benzyne lead to especially rapid and high yield of this subsequent reaction.
785:
712:
683:
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527:
et al. invoked zwitterionic intermediate in the reaction of fluorobenzene and phenyllithium to give biphenyl. This hypothesis was later confirmed.
2382:
Soorukram, D.; Qu, T.; Barrett, A. G. M. (2008). "Four-Component
Benzyne Coupling Reactions: A Concise Total Synthesis of Dehydroaltenuene B".
1345:
Mizukoshi, Yoshihide; Mikami, Koichiro; Uchiyama, Masanobu (2015). "Aryne
Polymerization Enabling Straightforward Synthesis of Elusive Poly(
541:
et al. showed that the reaction of chlorobenzene-1-C and potassium amide gave equal amounts of aniline with C incorporation at C-1 and C-2.
2285:
Galm, U; Hager, MH; Van Lanen, SG; Ju, J; Thorson, JS; Shen, B (Feb 2005). "Antitumor antibiotics: bleomycin, enediynes, and mitomycin".
563:
Additional evidence for the existence of benzyne came from spectroscopic studies. Benzyne has been observed in a "molecular container".
555:
544:
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If benzyne is 1,2-didehydrobenzene, two further isomers are possible: 1,3-didehydrobenzene and 1,4-didehydrobenzene. Their energies
63:
The alkyne representation of benzyne is the most widely encountered. Arynes are usually described as having a strained triple bond.
1029:
Logullo, Francis M.; Seitz, Arnold M.; Friedman, Lester (1968). "Benzenediazonium-2-Carboxylate and
Biphenylene (Benzenediazonium,
1615:"Use of 1,2,4,5-Tetrabromobenzene as a 1,4-Nenzadiyne Equivalent: Anti- and Syn-1,4,5,8-tetrahydroanthracene 1,4:5,8-diepoxides".
1748:
Blake, M. E.; Bartlett, K. L.; Jones, M. Jr (2003). "A m-Benzyne to o-Benzyne
Conversion Through a 1,2-Shift of a Phenyl Group".
1441:
Im, G-Yoon J.; Bronner, Sarah M.; Goetz, Adam E.; Paton, Robert S.; Cheong, Paul H.-Y.; Houk, K. N.; Garg, Neil K. (2010-12-22).
1443:"Indolyne Experimental and Computational Studies: Synthetic Applications and Origins of Selectivities of Nucleophilic Additions"
393:
Mori and co-workers performed a palladium-catalyzed -cocyclization of aryne and diyne in their total synthesis of taiwanins C.
2242:
On-surface; Pérez, E.Guitián; Peña, L.Gross (2015). "On-surface generation and imaging of arynes by atomic force microscopy".
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resulting in regioisomer B being generated. Analogously, if Y is electron donating, regioisomer A is generated, since now H
1272:
886:
Radziszewski, J. G.; Hess, B. A. Jr.; Zahradnik, R. (1992). "Infrared
Spectrum of o-Benzyne: Experiment and Theory".
1644:"Concise Total Synthesis of (±)-cis-Trikentrin A and (±)-Herbindole A via Intermolecular Indole Aryne Cycloaddition"
659:
445:
substituted aryne precursors as shown below. Extremely high temperatures are required for benzyne interconversion.
175:
146:
can be converted to 2-diazoniobenzene-1-carboxylate by diazotization and neutralization. Although explosive, this
2441:
1384:
Cheong, Paul H.-Y.; Paton, Robert S.; Bronner, Sarah M.; Im, G-Yoon J.; Garg, Neil K.; Houk, K. N. (2010-02-03).
983:
Sullivan, John M. (1971-06-01). "Explosion during preparation of benzenediazonium-2-carboxylate hydrochloride".
2451:
342:
1073:
Tadross, P. M.; Stoltz, B. M. (2012). "A Comprehensive
History of Arynes in Natural Product Total Synthesis".
567:
488:
is formed can only be explained by a presence of a cyclic and symmetrical intermediate–1,4-didehydrobenzene.
200:
1986:
Wittig, Georg (1942). "Phenyl-lithium, der Schlüssel zu einer neuen Chemie metallorganischer Verbindungen".
516:
234:
Upon treatment with basic nucleophiles, aryl halides deprotonate alpha to the leaving group, resulting in
259:
360:
2067:
Roberts, John D. (1953). "Rearrangement in the Reaction of Chlorobenzene-1-C14With Potassium Amide1".
1500:"The Role of Aryne Distortions, Steric Effects, and Charges in Regioselectivities of Aryne Reactions"
346:
266:
as the initiator to add to the first aryne yielded polymers containing up to about 100 arene units.
1211:(1969). "Reactive intermediates. Part I. Synthesis and oxidation of 1- and 2-aminobenzotriazole".
369:
6,7-indolyne undergoes cycloaddition with cyclopentadiene to afford complex tetracyclic product.
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32:
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Day, J. J.; McFadden, R. M.; Virgil, S. C.; Kolding, H.; Alleva, J. L.; Stoltz, B. M. (2011).
1264:
1257:
2446:
851:
Gampe, C. M.; Carreira, E. M. (2012). "Arynes and Cyclohexyne in Natural Product Synthesis".
751:
Hans Henning Wenk; Michael Winkler; Wolfram Sander (2003). "One Century of Aryne Chemistry".
207:
generates an intermediate which can be oxidised to benzyne in almost quantitative yield with
109:
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1995:
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The first example of aryne σ-bond insertion reaction is the synthesis of melleine in 1973.
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In 1953 C labeling experiments provided strong support for the intermediacy of benzyne.
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triplet, and therefore some of the stabilizing energy will be lost in order to form the
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1263:. Richardson, Kathleen Schueller (3rd ed.). New York: Harper & Row. pp.
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aryne was used in the attempted synthesis of cryptaustoline (1) and cryptowoline (2).
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Breakthroughs on 1,4-didehydrobenzene came in the 1960s, followed from studies on the
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Roberts, John D. (1956). "Orientation in Aminations of Substituted Halobenzenes 1".
2015:
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600:. This theme became topical with the discovery of enediyne "cytostatics", such as
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1244:. Pasadena, CA: California Institute of Technology (Ph.D. Thesis). pp. 4–5.
1125:
2150:. Edited by Lutz Ackermann 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
2029:
Wittig, G (1954). "Fortschritte auf dem Gebiet der organischen Aniono-Chemie".
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Wittig and Pohmer found that benzyne participate in cycloaddition reactions.
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794:, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "
721:, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "
692:, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "
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Medina, Jose M.; Mackey, Joel L.; Garg, Neil K.; Houk, K. N. (2014-11-05).
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Warmuth, R.; Yoon (2001). "Recent highlights in hemicarcerand chemistry".
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Roberts, John D. (1956). "The Mechanism of Aminations of Halobenzenes 1".
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66:
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Hoye, T. R.; Baire, B.; Niu, D.; Willoughby, P. H.; Woods, B. P. (2012).
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The Elimination-Addition Mechanism of Nucleophilic Aromatic Substitution
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In classical 1,4-didehydrobenzene experiments, heating to 300 °C, -
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916:. Patai, S.; Rappaport, Z. Eds., John Wiley & Sons, New York, 1983
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Organic compound made by removing substituents from an aromatic ring
1386:"Indolyne and Aryne Distortions and Nucleophilic Regioselectivites"
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1979:
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The metal–arene product can also add to another aryne, leading to
1812:
1110:"o -Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors"
2335:"The catalytic enantioselective total synthesis of (+)-liphagal"
92:
2420:
1961:
Berichte der Deutschen Chemischen Gesellschaft (A and B Series)
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442:
167:
153:
134:
48:
828:-benzyne" as erroneous terms for 1,3- and 1,4-didehydrobenzene
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species is a convenient and inexpensive precursor to benzyne.
354:
2167:
Heaney, H. (1962). "The Benzyne and Related Intermediates".
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C labeling experiment shows equal distribution of products.
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Due to their extreme reactivity, arynes must be generated
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Capture of benzyne as dienophile in Diels-Alder reaction.
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372:
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cyclization reactions. When generated in the presence of
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914:
The Chemistry of Triple Bonded Functional Groups, Part 1
476:. The simultaneous migration of deuterium atoms to form
411:
1897:"Design of Diradical-based Hydrogen Abstraction Agents"
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178:(HDDA) involves cycloaddition of 1,3-diyne and alkyne.
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1958:
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Diemer, V.; Begaut, M.; Leroux, F. R.; Colobert, F.
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1108:Shi, Jiarong; Li, Lianggui; Li, Yang (2021-04-14).
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566:In 2015, a single aryne molecule was imaged by
1934:Berichte der Deutschen Chemischen Gesellschaft
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160:Another method is based on trimethylsilylaryl
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1295:: CS1 maint: multiple names: authors list (
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1642:Buszek, K. R.; Brown, N.; Kuo, D. (2009).
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604:, which generates a 1,4-didehydrobenzene.
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1259:Mechanism and theory in organic chemistry
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2123:Journal of the American Chemical Society
2096:Journal of the American Chemical Society
2069:Journal of the American Chemical Society
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1504:Journal of the American Chemical Society
1447:Journal of the American Chemical Society
1390:Journal of the American Chemical Society
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112:, benzyne must be trapped, otherwise it
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841:, University Science Books, 2006, p612.
608:Examples of benzynes in total synthesis
99:
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2166:
2028:
1985:
1149:"The hexadehydro-Diels–Alder reaction"
955:
946:
735:
650:More examples use of aryne chemistry:
455:
341:A classic example is the synthesis of
221:
1239:
1894:
1803:
1033:-carboxy-, hydroxide, inner salt)".
956:Wittig, Georg (1959). "Triptycene".
58:
13:
1928:Stoermer, R.; Kahlert, B. (1902).
1588:"1,2,3,4-Tetraphenylnaphthalene".
1555:Heaney, H.; Millar, I. T. (1960).
1314:Modern Physical Organic Chemistry.
1254:
791:Compendium of Chemical Terminology
718:Compendium of Chemical Terminology
689:Compendium of Chemical Terminology
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1930:"Ueber das 1- und 2-Brom-cumaron"
1576:, vol. 5, 1973, p. 1120
839:Modern Physical Organic Chemistry
837:Anslyn, E. V.; Dougherty, D. A.:
820:entry for "benzynes" identifies "
634:synthesis of dehydroaltenuene B.
123:Early routes to benzyne involved
2419:
1703:Stevens, R. V.; Bisacchi, G. S.
1312:Anslyn, E. V.; Dougherty, D. A.
660:Transition metal benzyne complex
468:, but does not equilibrate with
230:Nucleophilic additions to arynes
176:hexadehydro Diels-Alder reaction
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912:Gilchrist, T. L. Supplement C:
357:to form a tetrahydroanthracene
1716:Sato, Y.; Tamura,T.; Mori, M.
906:
879:
844:
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706:
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343:1,2,3,4-tetraphenylnaphthalene
305:Pericyclic reactions of arynes
1:
1690:Pellissier, H.; Santelli, M.
985:Journal of Chemical Education
671:
520:First indication of benzyne.
480:, and the fact that none of
7:
1126:10.1021/acs.chemrev.0c01011
644:
464:readily equilibrates with -
364:diaryne reaction with furan
282:is the more acidic proton.
260:chain-growth polymerization
10:
2468:
1901:Angew. Chem. Int. Ed. Engl
1316:University Science Books,
1255:H., Lowry, Thomas (1987).
853:Angew. Chem. Int. Ed. Engl
507:
2148:Modern Arylation Methods
2051:10.1002/ange.19540660103
1973:10.1002/cber.19400731113
1946:10.1002/cber.19020350286
1629:10.15227/orgsyn.075.0201
1602:10.15227/orgsyn.046.0107
1047:10.15227/orgsyn.048.0012
970:10.15227/orgsyn.039.0075
664:The pyridine equivalent
2193:Wittig, G.; Pohmer, L.
1988:Die Naturwissenschaften
804:10.1351/goldbook.D01574
731:10.1351/goldbook.B00634
702:10.1351/goldbook.A00465
2442:Reactive intermediates
2351:10.1002/anie.201101842
1914:10.1002/anie.199614781
1240:Panar, Manuel (1961).
865:10.1002/anie.201107485
765:10.1002/anie.200390151
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110:reactive intermediates
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31:are a class of highly
2452:Aromatic hydrocarbons
1729:Guyot, M.; Molho, D.
1718:Angew. Chem. Int. Ed.
640:
629:
619:
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441:(900 °C) of the
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419:Other dehydrobenzenes
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320:Benzynes can undergo
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274:is more acidic than H
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2428:at Wikimedia Commons
2339:Angew. Chem. Int. Ed
1227:10.1039/J39690000742
753:Angew. Chem. Int. Ed
100:Generation of arynes
2256:2015NatCh...7..623P
2181:10.1021/cr60216a001
2135:10.1021/ja01584a025
2108:10.1021/ja01584a024
2081:10.1021/ja01109a523
2043:1954AngCh..66...10W
2000:1942NW.....30..696W
1882:10.1021/ar00021a001
1855:10.1021/ja00027a014
1828:10.1021/ja00757a071
1510:(44): 15798–15805.
1453:(50): 17933–17944.
1173:10.1038/nature11518
1165:2012Natur.490..208H
1005:10.1021/ed048p419.3
997:1971JChEd..48..419S
940:10.1021/ja01008a018
900:10.1021/ja00027a007
656:in-methylcyclophane
652:tricyclobutabenzene
598:Bergman cyclization
456:1,4-Didehydroarenes
236:dehydrohalogenation
222:Reactions of arynes
125:dehydrohalogenation
108:. Typical of other
2264:10.1038/nchem.2300
2197:1955; 67(13), 348.
2008:10.1007/BF01489519
1994:(46–47): 696–703.
1785:J. Phys. Org. Chem
1330:Eur. J. Org. Chem.
642:
631:
621:
561:
550:
535:
522:
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453:
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377:
366:
339:
290:
256:
246:
219:
186:
172:
158:
139:
97:
82:
71:
43:by removal of two
2424:Media related to
2396:10.1021/ol8015435
2390:(17): 3833–3835.
2299:10.1021/cr030117g
2221:10.1021/ar980082k
2156:978-3-527-31937-4
2075:(13): 3290–3291.
2031:Angewandte Chemie
1967:(11): 1193–1197.
1816:J. Am. Chem. Soc.
1762:10.1021/ja0213672
1731:Tetrahedron Lett.
1660:10.1021/ol802425m
1617:Organic Syntheses
1590:Organic Syntheses
1574:Collected Volumes
1562:Organic Syntheses
1516:10.1021/ja5099935
1459:10.1021/ja1086485
1402:10.1021/ja9098643
1363:10.1021/ja5112207
1159:(7419): 208–212.
1087:10.1021/cr200478h
347:Tetrabromobenzene
264:copper(I) cyanide
59:Bonding in arynes
21:organic chemistry
2459:
2423:
2408:
2407:
2379:
2373:
2372:
2362:
2330:
2324:
2321:J. Chem. Soc., C
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2287:Chemical Reviews
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2244:Nature Chemistry
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2054:
2026:
2020:
2019:
1983:
1977:
1976:
1956:
1950:
1949:
1940:(2): 1633–1640.
1925:
1919:
1918:
1916:
1895:Chen, P (1996).
1892:
1886:
1885:
1865:
1859:
1858:
1843:J. Am. Chem. Soc
1838:
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1396:(4): 1267–1269.
1381:
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1207:Campbell, C.D.;
1204:
1195:
1194:
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1120:(7): 3892–4044.
1114:Chemical Reviews
1105:
1099:
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1081:(6): 3550–3577.
1070:
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888:J. Am. Chem. Soc
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748:
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501:transition state
209:lead(IV) acetate
144:Anthranilic acid
39:derived from an
2467:
2466:
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1984:
1980:
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1797:10.1002/poc.797
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1756:(21): 6485–90.
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981:
977:
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947:
924:
920:
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907:
884:
880:
859:(16): 3766–78.
849:
845:
836:
832:
824:-benzyne" and "
813:
809:
784:
780:
749:
736:
711:
707:
682:
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647:
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592:
588:
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539:John D. Roberts
510:
458:
421:
406:
349:can react with
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281:
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232:
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102:
61:
17:
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5:
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2414:External links
2412:
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2374:
2345:(30): 6814–8.
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2234:
2209:Acc. Chem. Res
2199:
2186:
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2129:(3): 611–614.
2113:
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2086:
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2021:
1978:
1951:
1920:
1907:(1314): 1478.
1887:
1870:Acc. Chem. Res
1860:
1833:
1822:(2): 660–661.
1802:
1791:(9): 798–806.
1775:
1735:
1733:1973; 14, 3433
1722:
1720:2004; 43, 2436
1709:
1707:1982; 47, 2396
1696:
1683:
1654:(1): 201–204.
1634:
1607:
1580:
1557:"Triphenylene"
1547:
1490:
1433:
1376:
1337:
1321:
1302:
1273:
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1232:
1221:(5): 742–747.
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205:-sulfonic acid
201:hydroxylamine-
197:-benzotriazole
191:-amination of
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1623:: 201. 1998.
1622:
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1599:
1596:: 107. 1966.
1595:
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1349:-arylene)s".
1348:
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56:
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50:
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42:
41:aromatic ring
38:
34:
30:
26:
22:
2447:Cycloalkynes
2387:
2383:
2377:
2342:
2338:
2328:
2320:
2315:
2290:
2286:
2280:
2250:(8): 623–8.
2247:
2243:
2237:
2212:
2208:
2202:
2195:Angew. Chem.
2194:
2189:
2175:(2): 81–97.
2172:
2168:
2162:
2147:
2143:
2126:
2122:
2116:
2099:
2095:
2089:
2072:
2068:
2037:(1): 10–17.
2034:
2030:
2024:
1991:
1987:
1981:
1964:
1960:
1954:
1937:
1933:
1923:
1904:
1900:
1890:
1873:
1869:
1863:
1846:
1842:
1836:
1819:
1814:
1788:
1784:
1778:
1753:
1749:
1730:
1725:
1717:
1712:
1704:
1699:
1692:Tetrahedron,
1691:
1686:
1651:
1647:
1637:
1620:
1616:
1610:
1593:
1589:
1583:
1573:
1566:
1560:
1550:
1507:
1503:
1493:
1450:
1446:
1436:
1393:
1389:
1379:
1357:(1): 74–77.
1354:
1350:
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1340:
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1313:
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481:
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465:
461:
459:
436:
422:
407:
392:
381:
378:
367:
351:butyllithium
340:
319:
315:triphenylene
308:
291:
268:
257:
247:
233:
225:
202:
194:
188:
187:
173:
159:
148:zwitterionic
140:
129:aryl halides
122:
105:
103:
83:
72:
62:
45:substituents
28:
24:
18:
934:(6): 1499.
118:biphenylene
51:under high
2436:Categories
2323:1967, 2208
1876:(9): 385.
1035:Org. Synth
991:(6): 419.
958:Org. Synth
672:References
329:trypticene
325:anthracene
2384:Org. Lett
2215:(2): 96.
1648:Org. Lett
1524:0002-7863
1467:0002-7863
1410:0002-7863
1291:cite book
1209:C.W. Rees
1134:0009-2665
1075:Chem. Rev
1013:0021-9584
817:Gold Book
439:pyrolysis
425:in silico
162:triflates
114:dimerises
35:chemical
2404:18672878
2369:21671325
2307:15700963
2272:26201737
2229:11263868
2016:37148502
1770:12785789
1678:19055375
1542:25303232
1485:21114321
1428:20058924
1371:25459083
1283:14214254
1191:23060191
1095:22443517
873:22422638
773:12569480
723:Benzynes
666:pyridyne
645:See also
262:. Using
33:reactive
29:benzynes
2360:3361906
2252:Bibcode
2039:Bibcode
1996:Bibcode
1669:2723800
1533:4221504
1476:3075889
1419:2819077
1182:3538845
1161:Bibcode
993:Bibcode
508:History
106:in situ
49:alkynes
37:species
2426:Arynes
2402:
2367:
2357:
2305:
2270:
2227:
2154:
2014:
1849:: 99.
1768:
1676:
1666:
1540:
1530:
1522:
1483:
1473:
1465:
1426:
1416:
1408:
1369:
1281:
1271:
1189:
1179:
1153:Nature
1132:
1093:
1041:: 12.
1011:
964:: 75.
894:: 52.
871:
814:IUPAC
771:
585:C(O)CH
525:Wittig
443:phenyl
313:gives
53:strain
25:arynes
2012:S2CID
1569:: 105
1347:ortho
1335:, 341
786:IUPAC
713:IUPAC
694:Aryne
684:IUPAC
355:furan
199:with
2400:PMID
2365:PMID
2303:PMID
2268:PMID
2225:PMID
2152:ISBN
1766:PMID
1674:PMID
1538:PMID
1520:ISSN
1481:PMID
1463:ISSN
1424:PMID
1406:ISSN
1367:PMID
1333:2011
1318:2006
1297:link
1279:OCLC
1269:ISBN
1219:1969
1187:PMID
1130:ISSN
1091:PMID
1009:ISSN
869:PMID
769:PMID
353:and
299:Garg
297:and
295:Houk
86:LUMO
84:The
27:and
2392:doi
2355:PMC
2347:doi
2295:doi
2291:105
2260:doi
2217:doi
2177:doi
2131:doi
2104:doi
2077:doi
2047:doi
2004:doi
1969:doi
1942:doi
1909:doi
1878:doi
1851:doi
1847:114
1824:doi
1793:doi
1758:doi
1754:125
1664:PMC
1656:doi
1625:doi
1598:doi
1528:PMC
1512:doi
1508:136
1471:PMC
1455:doi
1451:132
1414:PMC
1398:doi
1394:132
1359:doi
1355:137
1265:643
1223:doi
1177:PMC
1169:doi
1157:490
1122:doi
1118:121
1083:doi
1079:112
1043:doi
1001:doi
966:doi
936:doi
896:doi
892:114
861:doi
800:doi
798:".
761:doi
727:doi
725:".
698:doi
696:".
568:STM
484:or
472:or
127:of
116:to
19:In
2438::
2398:.
2388:10
2386:.
2363:.
2353:.
2343:50
2341:.
2337:.
2301:.
2289:.
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