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Claisen rearrangement#Johnson.E2.80.93Claisen rearrangement

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Claisen rearrangement#Johnson.E2.80.93Claisen rearrangement
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{{Use dmy dates|date=May 2013}}{hide}Reactionbox| Name = Claisen rearrangement| Type = Rearrangement reaction| NamedAfter = Rainer Ludwig Claisen| Section3 = {{Reactionbox Identifiers
| OrganicChemistryNamed = claisen-rearrangement
| RSC_ontology_id = 0000148
{edih}
}}The Claisen rearrangement (not to be confused with the Claisen condensation) is a powerful carbon–carbon bond-forming chemical reaction discovered by Rainer Ludwig Claisen. The heating of an allyl vinyl ether will initiate a [3,3]-sigmatropic rearrangement to give a γ,δ-unsaturated carbonyl.
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- Claisen Rearrangement Scheme.png -
center|233xThe Claisen rearrangement
Discovered in 1912, the Claisen rearrangement is the first recorded example of a [3,3]-sigmatropic rearrangement.JOURNAL, Claisen, L., Chemische Berichte, 1912, 45, 3157–3166,weblink 10.1002/cber.19120450348, Über Umlagerung von Phenol-allyläthern in C-Allyl-phenole, 3, JOURNAL, Claisen, L., Tietze, E., Chemische Berichte, 1925, 58, 275, 10.1002/cber.19250580207, Über den Mechanismus der Umlagerung der Phenol-allyläther, 2, JOURNAL, Claisen, L., Tietze, E., Chemische Berichte, 1926, 59, 2344, 10.1002/cber.19260590927, Über den Mechanismus der Umlagerung der Phenol-allyläther. (2. Mitteilung), 9, Many reviews have been written.Hiersemann, M.; Nubbemeyer, U. (2007) The Claisen Rearrangement. Wiley-VCH. {{ISBN|3-527-30825-3}}JOURNAL, Rhoads, S. J., Raulins, N. R., 10.1002/0471264180.or022.01, Org. React., 1975, 22, 1–252, The Claisen and Cope Rearrangements, 0471264180, JOURNAL, Ziegler, F. E., Chem. Rev., 1988, 88, 1423–1452, 10.1021/cr00090a001, The thermal, aliphatic Claisen rearrangement, 8, JOURNAL, Wipf, P., Compr. Org. Synth., 1991, 5, 827–873, 10.1016/B978-0-08-052349-1.00140-2, Claisen Rearrangements, 978-0-08-052349-1,

Mechanism

The Claisen rearrangement is an exothermic, concerted (bond cleavage and recombination) pericyclic reaction. Woodward–Hoffmann rules show a suprafacial, stereospecific reaction pathway. The kinetics are of the first order and the whole transformation proceeds through a highly ordered cyclic transition state and is intramolecular. Crossover experiments eliminate the possibility of the rearrangement occurring via an intermolecular reaction mechanism and are consistent with an intramolecular process.JOURNAL, 1937, Observations on the Rearrangement of Allyl Aryl Ethers, J. Am. Chem. Soc., 59, 107, 10.1021/ja01280a024, Hurd, C. D., Schmerling, L., BOOK,weblink Advanced Organic Chemistry: Part A: Structure and Mechanisms, Springer, 2007, 978-0-387-44897-8, 934–935, Francis A. Carey, Richard J. Sundberg, There are substantial solvent effects observed in the Claisen rearrangement, where polar solvents tend to accelerate the reaction to a greater extent. Hydrogen-bonding solvents gave the highest rate constants. For example, ethanol/water solvent mixtures give rate constants 10-fold higher than sulfolane.JOURNAL, 1912, Über Umlagerung von Phenol-allyläthern in C-Allyl-phenole,weblink Chemische Berichte, 45, 3, 3157–3166, 10.1002/cber.19120450348, Claisen, L., JOURNAL, 1925, Über den Mechanismus der Umlagerung der Phenol-allyläther, Chemische Berichte, 58, 2, 275, 10.1002/cber.19250580207, Claisen, L., Tietze, E., Trivalent organoaluminium reagents, such as trimethylaluminium, have been shown to accelerate this reaction.JOURNAL, 1958, A Kinetic Study of the ortho-Claisen Rearrangement1, J. Am. Chem. Soc., 80, 13, 3277, 10.1021/ja01546a024, Goering, H. L., Jacobson, R. R., JOURNAL, 1970, The o-Claisen rearrangement. VIII. Solvent effects, J. Org. Chem., 35, 7, 2196, 10.1021/jo00832a019, White, W. N., Wolfarth, E. F.,

Variations

Aromatic Claisen rearrangement

The first reported Claisen rearrangement is the [3,3]-sigmatropic rearrangement of an allyl phenyl ether to intermediate 1, which quickly tautomerizes to an ortho-substituted phenol.(File:Aromatic_claisen_1.jpg|center|329x329px|The Claisen rearrangement)Meta-substitution affects the regioselectivity of this rearrangement.JOURNAL, White, William; and Slater, Carl, Slater, Carl D., 1961, The ortho-Claisen Rearrangement. V. The Products of Rearrangement of Allyl m-X-Phenyl Ethers, The Journal of Organic Chemistry, 26, 10, 3631–3638, 10.1021/jo01068a004, William N., JOURNAL, Gozzo, Fábio; Fernandes, Sergio; Rodrigues, Denise; Eberlin, Marcos; and Marsaioli, Anita, Fernandes, Sergio Antonio, Rodrigues, Denise Cristina, Eberlin, Marcos Nogueira, Marsaioli, Anita Jocelyne, 2003, Regioselectivity in Aromatic Claisen Rearrangements, The Journal of Organic Chemistry, 68, 14, 5493–5499, 10.1021/jo026385g, 12839439, Fábio Cesar, For example, electron withdrawing groups (e.g. bromide) at the meta-position direct the rearrangement to the ortho-position (71% ortho-product), while electron donating groups (e.g. methoxy), direct rearrangement to the para-position (69% para-product). Additionally, presence of ortho-substituents exclusively leads to para-substituted rearrangement products (tandem Claisen and Cope rearrangement).BOOK,weblink Strategic Applications Of Named Reactions In Organic Synthesis: Background And Detailed Mechanics: 250 Named Reactions, Academic Press, 2005, 978-0-12-429785-2, László Kürti, Barbara Czakó, 27 March 2013, (File:Aromatic_Claisen_with_ortho-position_Substituted.png|center|549x549px|Aromatic Claisen with ortho-position substituted)If an aldehyde or carboxylic acid occupies the ortho or para positions, the allyl side-chain displaces the group, releasing it as carbon monoxide or carbon dioxide, respectively.BOOK,weblink Organic Reactions, Volume II, Adams, Rodger, John Wiley & Sons, Inc., 1944, Newyork, 11–12, JOURNAL, Claisen, L., 1913, Über die Umlagerung von Phenolallyläthern in die isomeren Allylphenole, Justus Liebigs Annalen der Chemie, 401, 1, 90, 10.1002/jlac.19134010103, Eisleb, O.,

Bellus–Claisen rearrangement

The Bellus–Claisen rearrangement is the reaction of allylic ethers, amines, and thioethers with ketenes to give γ,δ-unsaturated esters, amides, and thioesters.JOURNAL, 1978, A New Type of Claisen Rearrangement Involving 1,3-Dipolar Intermediates. Preliminary communication, Helv. Chim. Acta, 61, 8, 3096–3099, 10.1002/hlca.19780610836, Malherbe, R., Bellus, D., JOURNAL, 1983, Reactions of haloketenes with allyl ethers and thioethers: A new type of Claisen rearrangement, J. Org. Chem., 48, 6, 860–869, 10.1021/jo00154a023, Malherbe, R., Rist, G., Bellus, D., JOURNAL, 2004, The Belluš–Claisen Rearrangement, Angew. Chem. Int. Ed., 43, 27, 3516–3524, 10.1002/anie.200301718, Gonda, J., This transformation was serendipitously observed by Bellus in 1979 through their synthesis of a key intermediate of an insecticide, pyrethroid. Halogen substituted ketenes (R1, R2) are often used in this reaction for their high electrophilicity. Numerous reductive methods for the removal of the resulting α-haloesters, amides and thioesters have been developed.JOURNAL, Edstrom, E, 1991, An unexpected reversal in the stereochemistry of transannular cyclizations. A stereoselective synthesis of (±)-epilupinine.,weblink Tetrahedron Letters, 10.1016/S0040-4039(00)93536-6, JOURNAL, Bellus, 1983, Reactions of haloketenes with allyl ethers and thioethers: a new type of Claisen rearrangement,weblink JOC, 10.1021/jo00154a023, The Bellus-Claisen offers synthetic chemists a unique opportunity for ring expansion strategies.
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- Claisen Bellus Rearrangement.png -
center|442xThe Bellus–Claisen rearrangement

Eschenmoser–Claisen rearrangement

The Eschenmoser–Claisen rearrangement proceeds by heating allylic alcohols in the presence of N,N-dimethylacetamide dimethyl acetal to form γ,δ-unsaturated amide. This was developed by Albert Eschenmoser in 1964.JOURNAL, 1964, CLAISEN'sche Umlagerungen bei Allyl- und Benzylalkoholen mit Hilfe von Acetalen des N, N-Dimethylacetamids. Vorläufige Mitteilung, Helv. Chim. Acta, 47, 8, 2425–2429, 10.1002/hlca.19640470835, Wick, A. E., Felix, D., Steen, K., Eschenmoser, A., JOURNAL, 1969, CLAISEN'sche Umlagerungen bei Allyl- und Benzylalkoholen mit 1-Dimethylamino-1-methoxy-äthen, Helv. Chim. Acta, 52, 4, 1030–1042, 10.1002/hlca.19690520418, Wick, A. E., Felix, D., Gschwend-Steen, K., Eschenmoser, A., Eschenmoser-Claisen rearrangement was used as a key step in the total synthesis of morphine.JOURNAL, Guillou, C, 2008, Diastereoselective Total Synthesis of (±)-Codeine,weblink Chem. Eur. J., 10.1002/chem.200800744,
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- Eschenmoser-Claisen Rearrangement Scheme.png -
center|393xThe Eschenmoser-Claisen rearrangement
Mechanism:(File:Eschenmoser Claisen Mechanism.png|center|768x768px|Eschenmoser–Claisen mechanism)

Ireland–Claisen rearrangement

The Ireland–Claisen rearrangement is the reaction of an allylic carboxylate with a strong base (such as lithium diisopropylamide) to give a γ,δ-unsaturated carboxylic acid.JOURNAL, Mueller, R. H., 1972, Claisen rearrangement of allyl esters, Journal of the American Chemical Society, 94, 16, 5897, 10.1021/ja00771a062, R. E., Ireland, JOURNAL, 1975, The stereoselective generation of ester enolates, Tetrahedron Lett., 16, 46, 3975–3978, 10.1016/S0040-4039(00)91213-9, Ireland, R. E., Willard, A. K., JOURNAL, Mueller, R. H., Willard, A. K., 1976, The ester enolate Claisen rearrangement. Stereochemical control through stereoselective enolate formation, Journal of the American Chemical Society, 98, 10, 2868, 10.1021/ja00426a033, Ireland, R. E., The rearrangement proceeds via silylketene acetal, which is formed by trapping the lithium enolate with chlorotrimethylsilane. Like the Bellus-Claisen (above), Ireland-Claisen rearrangement can take place at room temperature and above. The E- and Z-configured silylketene acetals lead to anti and syn rearranged products, respectively.JOURNAL, Ireland, R. E., 1991, Stereochemical control in the ester enolate Claisen rearrangement.,weblink JOC, 10.1021/jo00002a030, There are numerous examples of enantioselective Ireland-Claisen rearrangements found in literature to include chiral boron reagents and the use of chiral auxiliaries.JOURNAL, Enders, E, 1996, Asymmetric [3.3]-sigmatropic rearrangements in organic synthesis,weblink Tetrahedron: Asymmetry, 10.1016/0957-4166(96)00220-0, JOURNAL, Corey, E, 1991, Highly enantioselective and diastereoselective Ireland-Claisen rearrangement of achiral allylic esters,weblink JACS, 10.1021/ja00010a074, (File:TOC_for_IC.jpg|center|466x466px|The Ireland–Claisen rearrangement)

{{anchor|Johnson-Claisen rearrangement}} Johnson–Claisen rearrangement

The Johnson–Claisen rearrangement is the reaction of an allylic alcohol with an orthoester to yield a {{no wrap|γ,δ-unsaturated}} ester.JOURNAL, Johnson, William Summer, Werthemann, Lucius, Bartlett, William R., Brocksom, Timothy J., Li, Tsung-Tee, Faulkner, D. John, Petersen, Michael R., 1970-02-01, Simple stereoselective version of the Claisen rearrangement leading to trans-trisubstituted olefinic bonds. Synthesis of squalene,weblink Journal of the American Chemical Society, 92, 3, 741–743, 10.1021/ja00706a074, 0002-7863, Weak acids, such as propionic acid, have been used to catalyze this reaction. This rearrangement often requires high temperatures (100 to 200 Â°C) and can take anywhere from 10 to 120 hours to complete.JOURNAL, Fernandes, R. A., 2013, The Orthoester Johnson–Claisen Rearrangement in the Synthesis of Bioactive Molecules, Natural Products, and Synthetic Intermediates – Recent Advances,weblink Eur JOC, 10.1002/ejoc.201301033, However, microwave assisted heating in the presence of KSF-clay or propionic acid have demonstrated dramatic increases in reaction rate and yields.JOURNAL, Huber, R. S., 1992, Acceleration of the orthoester Claisen rearrangement by clay catalyzed microwave thermolysis: expeditious route to bicyclic lactones,weblink JOC, 10.1021/jo00047a041, JOURNAL, Srikrishna, A, 1995, Application of microwave heating technique for rapid synthesis of γ,δ-unsaturated esters,weblink Tetrahedron, 10.1016/0040-4020(94)01058-8,
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- Johnson-Claisen Rearrangement Scheme.png -
center|The Johnson–Claisen rearrangement
Mechanism:(File:Johnson Claisen Mechanism.png|center|900px|Johnson–Claisen mechanism)

Photo-Claisen rearrangement

The photo-Claisen rearrangement is closely related to the photo-Fries rearrangement, that proceeds through a similar radical mechanism. Aryl ethers undergo the photo-Claisen rearrangement, while the photo-Fries rearrangement utilizes aryl esters.IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version:weblink (2006–) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. {{ISBN|0-9678550-9-8}}. {{DOI|10.1351/goldbook}}

Hetero-Claisens

Aza–Claisen

An iminium can serve as one of the pi-bonded moieties in the rearrangement.JOURNAL, Kurth, M. J., Decker, O. H. W., J. Org. Chem., 1985, 50, 5769–5775, 10.1021/jo00350a067, Enantioselective preparation of 3-substituted 4-pentenoic acids via the Claisen rearrangement, 26,
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- Aza-Claisen Rearrangement Example.png -
center|An example of the Aza–Claisen rearrangement

Chromium oxidation

Chromium can oxidize allylic alcohols to alpha-beta unsaturated ketones on the opposite side of the unsaturated bond from the alcohol. This is via a concerted hetero-Claisen reaction, although there are mechanistic differences since the chromium atom has access to d- shell orbitals which allow the reaction under a less constrained set of geometries.JOURNAL, Dauben, W. G., Michno, D. M., J. Org. Chem., 1977, 42, 682, 10.1021/jo00424a023, Direct oxidation of tertiary allylic alcohols. A simple and effective method for alkylative carbonyl transposition, 4, WEB,weblink (R)-(+)-3,4-DIMETHYLCYCLOHEX-2-EN-1-ONE [(R)-(+)-3,4-Dimethyl-2-cyclohexen-1-one], www.orgsyn.org, 2016-10-09,
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- ClaisenOx.png -
center

Chen–Mapp reaction

The Chen–Mapp reaction also known as the [3,3]-Phosphorimidate Rearrangement or Staudinger–Claisen Reaction installs a phosphite in the place of an alcohol and takes advantage of the Staudinger reduction to convert this to an imine. The subsequent Claisen is driven by the fact that a P=O double bond is more energetically favorable than a P=N double bond.JOURNAL, Chen, B., Mapp, A., Thermal and catalyzed 3,3-phosphorimidate rearrangements, Journal of the American Chemical Society, 127, 18, 6712–6718, 2005, 15869293, 10.1021/ja050759g,
missing image!
- MappReaction.png -
center|The Mapp reaction

Overman rearrangement

The Overman rearrangement (named after Larry Overman) is a Claisen rearrangement of allylic trichloroacetimidates to allylic trichloroacetamides.JOURNAL, Overman, L. E., Thermal and mercuric ion catalyzed [3,3]-sigmatropic rearrangement of allylic trichloroacetimidates. 1,3 Transposition of alcohol and amine functions, Journal of the American Chemical Society, 96, 2, 597–599, 1974, 10.1021/ja00809a054, JOURNAL, Overman, L. E., A general method for the synthesis of amines by the rearrangement of allylic trichloroacetimidates. 1,3 Transposition of alcohol and amine functions, Journal of the American Chemical Society, 98, 10, 2901–2910, 1976, 10.1021/ja00426a038, (Organic Syntheses]], Coll. Vol. 6, p.507; Vol. 58, p.4 (Article)
missing image!
- Overman Rearrangement scheme.svg|500px|center|The Overman rearrangement)Overman rearrangement is applicable to synthesis of vicinol diamino comp from 1,2 vicinal allylic diol.

Zwitterionic Claisen rearrangement

Unlike typical Claisen rearrangements which require heating, zwitterionic Claisen rearrangements take place at or below room temperature. The acyl ammonium ions are highly selective for Z-enolates under mild conditions.JOURNAL, Yu, C.-M., Choi, H.-S., Lee, J., Jung, W.-H., Kim, H.-J., J. Chem. Soc., Perkin Trans. 1, 1996, 115–116, 10.1039/p19960000115, Self-regulated molecular rearrangement: Diastereoselective zwitterionic aza-Claisen protocol, 2, JOURNAL, Nubbemeyer, U., J. Org. Chem., 1995, 60, 3773–3780, 10.1021/jo00117a032, 1,2-Asymmetric Induction in the Zwitterionic Claisen Rearrangement of Allylamines, 12, Zwitterionic Claisen Rearrangement Scheme.png
-

In nature

The enzyme chorismate mutase (EC 5.4.99.5) catalyzes the Claisen rearrangement of chorismate to prephenate, a key intermediate in the shikimate pathway (the biosynthetic pathway towards the synthesis of phenylalanine and tyrosine).JOURNAL, Ganem, B., Angew. Chem. Int. Ed. Engl., 1996, 35, 936–945, 10.1002/anie.199609361, The Mechanism of the Claisen Rearrangement: Déjà Vu All over Again, 9,
missing image!
- Chorismate Mutase Scheme.png -
center|Chorismate mutase catalyzes a Claisen rearrangement

See also

References

{{reflist|35em}}{{Authority control}}

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