Rearrangement reaction

Chemical reaction where a molecule is turned into a structural isomer of itself

In organic chemistry, a rearrangement reaction is a broad class of organic reactions where the carbon skeleton of a molecule is rearranged to give a structural isomer of the original molecule.[1] Often a substituent moves from one atom to another atom in the same molecule, hence these reactions are usually intramolecular. In the example below, the substituent R moves from carbon atom 1 to carbon atom 2:

− C | R − C − C − ⟶ − C − C | R − C − {\displaystyle {-}{\underset {| \atop \displaystyle \color {Blue}{\ce {R}}}{{\ce {C}}}}{\ce {-C-C{-}-> {-C-}}}{\underset {| \atop \displaystyle \color {Blue}{\ce {R}}}{{\ce {C}}}}{\ce {-C}}{-}}

Intermolecular rearrangements also take place.

A rearrangement is not well represented by simple and discrete electron transfers (represented by curved arrows in organic chemistry texts). The actual mechanism of alkyl groups moving, as in Wagner–Meerwein rearrangement, probably involves transfer of the moving alkyl group fluidly along a bond, not ionic bond-breaking and forming. In pericyclic reactions, explanation by orbital interactions give a better picture than simple discrete electron transfers. It is, nevertheless, possible to draw the curved arrows for a sequence of discrete electron transfers that give the same result as a rearrangement reaction, although these are not necessarily realistic. In allylic rearrangement, the reaction is indeed ionic.

Three key rearrangement reactions are 1,2-rearrangements, pericyclic reactions and olefin metathesis.

## 1,2-rearrangements[edit]

Main article: 1,2-rearrangement

A 1,2-rearrangement is an organic reaction where a substituent moves from one atom to another atom in a chemical compound. In a 1,2 shift the movement involves two adjacent atoms but moves over larger distances are possible. Skeletal isomerization is not normally encountered in the laboratory, but is the basis of large applications in oil refineries. In general, straight-chain alkanes are converted to branched isomers by heating in the presence of a catalyst. Examples include isomerisation of n-butane to isobutane and pentane to isopentane. Highly branched alkanes have favorable combustion characteristics for internal combustion engines.[2]

Further examples are the Wagner–Meerwein rearrangement:

and the Beckmann rearrangement,[3] which is relevant to the production of certain nylons:[4]

## Pericyclic reactions[edit]

Main article: pericyclic reactions

A pericyclic reaction is a type of reaction with multiple carbon–carbon bond making and breaking wherein the transition state of the molecule has a cyclic geometry, and the reaction progresses in a concerted fashion. Examples are hydride shifts

and the Claisen rearrangement:[5]

## Olefin metathesis[edit]

Main article: Olefin metathesis

Olefin metathesis is a formal exchange of the alkylidene fragments in two alkenes. It is a catalytic reaction with carbene, or more accurately, transition metal carbene complex intermediates.

In this example (ethenolysis, a pair of vinyl compounds form a new symmetrical alkene with expulsion of ethylene.

## Other rearragement reactions[edit]

### 1,3-rearrangements[edit]

1,3-rearrangements take place over 3 carbon atoms. Examples:

* the Fries rearrangement
* a 1,3-alkyl shift of verbenone to chrysanthenone

## See also[edit]

* Beckmann rearrangement
* Curtius rearrangement
* Hofmann rearrangement
* Lossen rearrangement
* Schmidt reaction
* Tiemann rearrangement
* Wolff rearrangement
* Photochemical rearrangements
* Thermal rearrangement of aromatic hydrocarbons
* Mumm rearrangement

## References[edit]

1. ^ March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 3rd edition, New York: Wiley, ISBN 9780471854722, OCLC 642506595
2. ^ Karl Griesbaum, Arno Behr, Dieter Biedenkapp, Heinz-Werner Voges, Dorothea Garbe, Christian Paetz, Gerd Collin, Dieter Mayer, Hartmut Höke (2002). "Hydrocarbons". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a13_227. ISBN 3527306730.`{{cite encyclopedia}}`: CS1 maint: uses authors parameter (link)
3. ^ Clayden, Jonathan; Greeves, Nick; Warren, Stuart (2012). Organic chemistry (2nd ed.). Oxford University Press. p. 958\. ISBN 978-0-19-927029-3.
4. ^ Nuyken, Oskar; Pask, Stephen (25 April 2013). "Ring-Opening Polymerization—An Introductory Review". Polymers. 5 (2): 361–403. doi:10.3390/polym5020361.
5. ^ Ziegler, Frederick E. (December 1988). "The thermal, aliphatic Claisen rearrangement". Chemical Reviews. 88 (8): 1423–1452. doi:10.1021/cr00090a001.

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Topics in organic reactions

* Addition reaction
* Elimination reaction
* Polymerization
* Reagents
* Rearrangement reaction
* Redox reaction
* Regioselectivity
* Stereoselectivity
* Stereospecificity
* Substitution reaction

* A value
* Alpha effect
* Annulene
* Anomeric effect
* Antiaromaticity
* Aromatic ring current
* Aromaticity
* Baird's rule
* Baker–Nathan effect
* Baldwin's rules
* Bema Hapothle
* Beta-silicon effect
* Bicycloaromaticity
* Bredt's rule
* Bürgi–Dunitz angle
* Catalytic resonance theory
* Charge remote fragmentation
* Charge-transfer complex
* Clar's rule
* Conformational isomerism
* Conjugated system
* Conrotatory and disrotatory
* Curtin–Hammett principle
* Dynamic binding (chemistry)
* Edwards equation
* Effective molarity
* Electromeric effect
* Electron-rich
* Electron-withdrawing group
* Electronic effect
* Electrophile
* Evelyn effect
* Flippin–Lodge angle
* Free-energy relationship
* Grunwald–Winstein equation
* Hammett acidity function
* Hammett equation
* George S. Hammond
* Hammond's postulate
* Homoaromaticity
* Hückel's rule
* Hyperconjugation
* Inductive effect
* Kinetic isotope effect
* LFER solvent coefficients (data page)
* Marcus theory
* Markovnikov's rule
* Möbius aromaticity
* Möbius–Hückel concept
* More O'Ferrall–Jencks plot
* Negative hyperconjugation
* Neighbouring group participation
* 2-Norbornyl cation
* Nucleophile
* Kennedy J. P. Orton
* Passive binding
* Phosphaethynolate
* Polar effect
* Polyfluorene
* Ring strain
* Σ-aromaticity
* Spherical aromaticity
* Spiroaromaticity
* Steric effects
* Superaromaticity
* Swain–Lupton equation
* Taft equation
* Thorpe–Ingold effect
* Vinylogy
* Walsh diagram
* Woodward–Hoffmann rules
* Woodward's rules
* Y-aromaticity
* Yukawa–Tsuno equation
* Zaitsev's rule
* Σ-bishomoaromaticity

List of organic reactions

Carbon-carbon
bond forming
reactions|

* Acetoacetic ester synthesis
* Acyloin condensation
* Aldol condensation
* Aldol reaction
* Alkane metathesis
* Alkyne metathesis
* Alkyne trimerisation
* Alkynylation
* Allan–Robinson reaction
* Arndt–Eistert reaction
* Auwers synthesis
* Aza-Baylis–Hillman reaction
* Barbier reaction
* Barton–Kellogg reaction
* Baylis–Hillman reaction
* Benary reaction
* Bergman cyclization
* Biginelli reaction
* Bingel reaction
* Blaise ketone synthesis
* Blaise reaction
* Blanc chloromethylation
* Bodroux–Chichibabin aldehyde synthesis
* Bouveault aldehyde synthesis
* Bucherer–Bergs reaction
* Buchner ring expansion
* Cadiot–Chodkiewicz coupling
* Carbonyl allylation
* Carbonyl olefin metathesis
* Castro–Stephens coupling
* Chan rearrangement
* Chan–Lam coupling
* Claisen condensation
* Claisen rearrangement
* Claisen-Schmidt condensation
* Combes quinoline synthesis
* Corey–Fuchs reaction
* Corey–House synthesis
* Coupling reaction
* Cross-coupling reaction
* Cross dehydrogenative coupling
* Cross-coupling partner
* Dakin–West reaction
* Darzens reaction
* Diels–Alder reaction
* Doebner reaction
* Wulff–Dötz reaction
* Ene reaction
* Enyne metathesis
* Ethenolysis
* Favorskii reaction
* Ferrier carbocyclization
* Friedel–Crafts reaction
* Fujimoto–Belleau reaction
* Fujiwara–Moritani reaction
* Fukuyama coupling
* Gabriel–Colman rearrangement
* Gattermann reaction
* Glaser coupling
* Grignard reaction
* Grignard reagent
* Hammick reaction
* Heck reaction
* Henry reaction
* Heterogeneous metal catalyzed cross-coupling
* High dilution principle
* Hiyama coupling
* Homologation reaction
* Horner–Wadsworth–Emmons reaction
* Hydrocyanation
* Hydrovinylation
* Hydroxymethylation
* Ivanov reaction
* Johnson–Corey–Chaykovsky reaction
* Julia olefination
* Julia–Kocienski olefination
* Kauffmann olefination
* Knoevenagel condensation
* Knorr pyrrole synthesis
* Kolbe–Schmitt reaction
* Kowalski ester homologation
* Kulinkovich reaction
* Kumada coupling
* Liebeskind–Srogl coupling
* Malonic ester synthesis
* Mannich reaction
* McMurry reaction
* Meerwein arylation
* Methylenation
* Michael reaction
* Minisci reaction
* Mizoroki-Heck vs. Reductive Heck
* Nef isocyanide reaction
* Nef synthesis
* Negishi coupling
* Nierenstein reaction
* Nitro-Mannich reaction
* Nozaki–Hiyama–Kishi reaction
* Olefin conversion technology
* Olefin metathesis
* Palladium–NHC complex
* Passerini reaction
* Peterson olefination
* Pfitzinger reaction
* Piancatelli rearrangement
* Pinacol coupling reaction
* Prins reaction
* Quelet reaction
* Ramberg–Bäcklund reaction
* Rauhut–Currier reaction
* Reformatsky reaction
* Reimer–Tiemann reaction
* Rieche formylation
* Ring-closing metathesis
* Robinson annulation
* Sakurai reaction
* Seyferth–Gilbert homologation
* Shapiro reaction
* Sonogashira coupling
* Stetter reaction
* Stille reaction
* Stollé synthesis
* Stork enamine alkylation
* Suzuki reaction
* Takai olefination
* Thermal rearrangement of aromatic hydrocarbons
* Thorpe reaction
* Ugi reaction
* Ullmann reaction
* Wagner-Jauregg reaction
* Weinreb ketone synthesis
* Wittig reaction
* Wurtz reaction
* Wurtz–Fittig reaction
* Zincke–Suhl reaction

| Homologation reactions|

* Arndt–Eistert reaction
* Hooker reaction
* Kiliani–Fischer synthesis
* Kowalski ester homologation
* Methoxymethylenetriphenylphosphorane
* Seyferth–Gilbert homologation
* Wittig reaction

|

Olefination reactions|

* Bamford–Stevens reaction
* Barton–Kellogg reaction
* Boord olefin synthesis
* Chugaev elimination
* Cope reaction
* Corey–Winter olefin synthesis
* Dehydrohalogenation
* Elimination reaction
* Grieco elimination
* Hofmann elimination
* Horner–Wadsworth–Emmons reaction
* Hydrazone iodination
* Julia olefination
* Julia–Kocienski olefination
* Kauffmann olefination
* McMurry reaction
* Peterson olefination
* Ramberg–Bäcklund reaction
* Shapiro reaction
* Takai olefination
* Wittig reaction

Carbon-heteroatom
bond forming
reactions|

* Azo coupling
* Bartoli indole synthesis
* Boudouard reaction
* Cadogan–Sundberg indole synthesis
* Diazonium compound
* Esterification
* Grignard reagent
* Haloform reaction
* Hegedus indole synthesis
* Hurd–Mori 1,2,3-thiadiazole synthesis
* Kharasch–Sosnovsky reaction
* Knorr pyrrole synthesis
* Leimgruber–Batcho indole synthesis
* Mukaiyama hydration
* Nenitzescu indole synthesis
* Oxymercuration reaction
* Reed reaction
* Schotten–Baumann reaction
* Ullmann condensation
* Williamson ether synthesis
* Yamaguchi esterification

Degradation
reactions|

* Barbier–Wieland degradation
* Bergmann degradation
* Edman degradation
* Emde degradation
* Gallagher–Hollander degradation
* Hofmann rearrangement
* Hooker reaction
* Isosaccharinic acid
* Marker degradation
* Ruff degradation
* Strecker degradation
* Von Braun amide degradation
* Weerman degradation
* Wohl degradation

Organic redox
reactions|

* Acyloin condensation
* Adkins–Peterson reaction
* Akabori amino-acid reaction
* Alcohol oxidation
* Algar–Flynn–Oyamada reaction
* Amide reduction
* Andrussow process
* Angeli–Rimini reaction
* Aromatization
* Autoxidation
* Baeyer–Villiger oxidation
* Barton–McCombie deoxygenation
* Bechamp reduction
* Benkeser reaction
* Bergmann degradation
* Birch reduction
* Bohn–Schmidt reaction
* Bosch reaction
* Bouveault–Blanc reduction
* Boyland–Sims oxidation
* Cannizzaro reaction
* Carbonyl reduction
* Clemmensen reduction
* Collins oxidation
* Corey–Itsuno reduction
* Corey–Kim oxidation
* Corey–Winter olefin synthesis
* Criegee oxidation
* Dakin oxidation
* Davis oxidation
* Deoxygenation
* Dess–Martin oxidation
* DNA oxidation
* Elbs persulfate oxidation
* Emde degradation
* Eschweiler–Clarke reaction
* Étard reaction
* Fischer–Tropsch process
* Fleming–Tamao oxidation
* Fukuyama reduction
* Ganem oxidation
* Glycol cleavage
* Griesbaum coozonolysis
* Grundmann aldehyde synthesis
* Haloform reaction
* Hydrogenation
* Hydrogenolysis
* Hydroxylation
* Jones oxidation
* Kiliani–Fischer synthesis
* Kolbe electrolysis
* Kornblum oxidation
* Kornblum–DeLaMare rearrangement
* Leuckart reaction
* Ley oxidation
* Lindgren oxidation
* Lipid peroxidation
* Lombardo methylenation
* Luche reduction
* Markó–Lam deoxygenation
* McFadyen–Stevens reaction
* Meerwein–Ponndorf–Verley reduction
* Methionine sulfoxide
* Miyaura borylation
* Mozingo reduction
* Noyori asymmetric hydrogenation
* Omega oxidation
* Oppenauer oxidation
* Oxygen rebound mechanism
* Ozonolysis
* Parikh–Doering oxidation
* Pinnick oxidation
* Prévost reaction
* Reduction of nitro compounds
* Reductive amination
* Riley oxidation
* Rosenmund reduction
* Rubottom oxidation
* Sabatier reaction
* Sarett oxidation
* Selenoxide elimination
* Shapiro reaction
* Sharpless asymmetric dihydroxylation
* Epoxidation of allylic alcohols
* Sharpless epoxidation
* Sharpless oxyamination
* Stahl oxidation
* Staudinger reaction
* Stephen aldehyde synthesis
* Swern oxidation
* Transfer hydrogenation
* Wacker process
* Wharton reaction
* Whiting reaction
* Wohl–Aue reaction
* Wolff–Kishner reduction
* Wolffenstein–Böters reaction
* Zinin reaction

Rearrangement
reactions|

* 1,2-rearrangement
* 1,2-Wittig rearrangement
* 2,3-sigmatropic rearrangement
* 2,3-Wittig rearrangement
* Achmatowicz reaction
* Alkyne zipper reaction
* Allen–Millar–Trippett rearrangement
* Allylic rearrangement
* Alpha-ketol rearrangement
* Amadori rearrangement
* Arndt–Eistert reaction
* Aza-Cope rearrangement
* Baker–Venkataraman rearrangement
* Bamberger rearrangement
* Banert cascade
* Beckmann rearrangement
* Benzilic acid rearrangement
* Bergman cyclization
* Bergmann degradation
* Boekelheide reaction
* Brook rearrangement
* Buchner ring expansion
* Carroll rearrangement
* Chan rearrangement
* Claisen rearrangement
* Cope rearrangement
* Corey–Fuchs reaction
* Cornforth rearrangement
* Criegee rearrangement
* Curtius rearrangement
* Demjanov rearrangement
* Di-π-methane rearrangement
* Dimroth rearrangement
* Divinylcyclopropane-cycloheptadiene rearrangement
* Dowd–Beckwith ring-expansion reaction
* Electrocyclic reaction
* Ene reaction
* Enyne metathesis
* Favorskii reaction
* Favorskii rearrangement
* Ferrier carbocyclization
* Ferrier rearrangement
* Fischer–Hepp rearrangement
* Fries rearrangement
* Fritsch–Buttenberg–Wiechell rearrangement
* Gabriel–Colman rearrangement
* Group transfer reaction
* Halogen dance rearrangement
* Hayashi rearrangement
* Hofmann rearrangement
* Hofmann–Martius rearrangement
* Ireland–Claisen rearrangement
* Jacobsen rearrangement
* Kornblum–DeLaMare rearrangement
* Kowalski ester homologation
* Lobry de Bruyn–Van Ekenstein transformation
* Lossen rearrangement
* McFadyen–Stevens reaction
* McLafferty rearrangement
* Meyer–Schuster rearrangement
* Mislow–Evans rearrangement
* Mumm rearrangement
* Myers allene synthesis
* Nazarov cyclization reaction
* Neber rearrangement
* Newman–Kwart rearrangement
* Overman rearrangement
* Oxy-Cope rearrangement
* Pericyclic reaction
* Piancatelli rearrangement
* Pinacol rearrangement
* Pummerer rearrangement
* Ramberg–Bäcklund reaction
* Ring expansion and contraction
* Ring-closing metathesis
* Rupe reaction
* Schmidt reaction
* Semipinacol rearrangement
* Seyferth–Gilbert homologation
* Sigmatropic reaction
* Skattebøl rearrangement
* Smiles rearrangement
* Sommelet–Hauser rearrangement
* Stevens rearrangement
* Stieglitz rearrangement
* Thermal rearrangement of aromatic hydrocarbons
* Tiffeneau–Demjanov rearrangement
* Vinylcyclopropane rearrangement
* Wagner–Meerwein rearrangement
* Wallach rearrangement
* Weerman degradation
* Westphalen–Lettré rearrangement
* Willgerodt rearrangement
* Wolff rearrangement

Ring forming
reactions|

* 1,3-Dipolar cycloaddition
* Annulation
* Azide-alkyne Huisgen cycloaddition
* Baeyer–Emmerling indole synthesis
* Bartoli indole synthesis
* Bergman cyclization
* Biginelli reaction
* Bischler–Möhlau indole synthesis
* Bischler–Napieralski reaction
* Blum–Ittah aziridine synthesis
* Bobbitt reaction
* Bohlmann–Rahtz pyridine synthesis
* Borsche–Drechsel cyclization
* Bucherer carbazole synthesis
* Bucherer–Bergs reaction
* Cadogan–Sundberg indole synthesis
* Camps quinoline synthesis
* Chichibabin pyridine synthesis
* Cook–Heilbron thiazole synthesis
* Cycloaddition
* Darzens reaction
* Davis–Beirut reaction
* De Kimpe aziridine synthesis
* Debus–Radziszewski imidazole synthesis
* Dieckmann condensation
* Diels–Alder reaction
* Feist–Benary synthesis
* Ferrario–Ackermann reaction
* Fiesselmann thiophene synthesis
* Fischer indole synthesis
* Fischer oxazole synthesis
* Friedländer synthesis
* Gewald reaction
* Graham reaction
* Hantzsch pyridine synthesis
* Hegedus indole synthesis
* Hemetsberger indole synthesis
* Hofmann–Löffler reaction
* Hurd–Mori 1,2,3-thiadiazole synthesis
* Iodolactonization
* Isay reaction
* Jacobsen epoxidation
* Johnson–Corey–Chaykovsky reaction
* Knorr pyrrole synthesis
* Knorr quinoline synthesis
* Kröhnke pyridine synthesis
* Kulinkovich reaction
* Larock indole synthesis
* Madelung synthesis
* Nazarov cyclization reaction
* Nenitzescu indole synthesis
* Niementowski quinazoline synthesis
* Niementowski quinoline synthesis
* Paal–Knorr synthesis
* Paternò–Büchi reaction
* Pechmann condensation
* Petrenko-Kritschenko piperidone synthesis
* Pictet–Spengler reaction
* Pomeranz–Fritsch reaction
* Prilezhaev reaction
* Pschorr cyclization
* Reissert indole synthesis
* Ring-closing metathesis
* Robinson annulation
* Sharpless epoxidation
* Simmons–Smith reaction
* Skraup reaction
* Urech hydantoin synthesis
* Van Leusen reaction
* Wenker synthesis

| Cycloaddition|

* 1,3-Dipolar cycloaddition
* 4+4 Photocycloaddition
* (4+3) cycloaddition
* 6+4 Cycloaddition
* Alkyne trimerisation
* Aza-Diels–Alder reaction
* Azide-alkyne Huisgen cycloaddition
* Bradsher cycloaddition
* Cheletropic reaction
* Conia-ene reaction
* Cyclopropanation
* Diazoalkane 1,3-dipolar cycloaddition
* Diels–Alder reaction
* Enone–alkene cycloadditions
* Hexadehydro Diels–Alder reaction
* Imine Diels–Alder reaction
* Intramolecular Diels–Alder cycloaddition
* Inverse electron-demand Diels–Alder reaction
* Ketene cycloaddition
* McCormack reaction
* Metal-centered cycloaddition reactions
* Nitrone-olefin (3+2) cycloaddition
* Oxo-Diels–Alder reaction
* Ozonolysis
* Pauson–Khand reaction
* Povarov reaction
* Prato reaction
* Retro-Diels–Alder reaction
* Staudinger synthesis
* Trimethylenemethane cycloaddition
* Vinylcyclopropane (5+2) cycloaddition
* Wagner-Jauregg reaction

|

Heterocycle forming reactions|

* Algar–Flynn–Oyamada reaction
* Allan–Robinson reaction
* Auwers synthesis
* Bamberger triazine synthesis
* Banert cascade
* Barton–Zard reaction
* Bernthsen acridine synthesis
* Bischler–Napieralski reaction
* Bobbitt reaction
* Boger pyridine synthesis
* Borsche–Drechsel cyclization
* Bucherer carbazole synthesis
* Bucherer–Bergs reaction
* Chichibabin pyridine synthesis
* Cook–Heilbron thiazole synthesis
* Diazoalkane 1,3-dipolar cycloaddition
* Einhorn–Brunner reaction
* Erlenmeyer–Plöchl azlactone and amino-acid synthesis
* Feist–Benary synthesis
* Fischer oxazole synthesis
* Gabriel–Colman rearrangement
* Gewald reaction
* Hantzsch ester
* Hantzsch pyridine synthesis
* Herz reaction
* Knorr pyrrole synthesis
* Kröhnke pyridine synthesis
* Lectka enantioselective beta-lactam synthesis
* Lehmstedt–Tanasescu reaction
* Niementowski quinazoline synthesis
* Nitrone-olefin (3+2) cycloaddition
* Paal–Knorr synthesis
* Pellizzari reaction
* Pictet–Spengler reaction
* Pomeranz–Fritsch reaction
* Prilezhaev reaction
* Robinson–Gabriel synthesis
* Stollé synthesis
* Urech hydantoin synthesis
* Wenker synthesis
* Wohl–Aue reaction

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