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A 1,2-rearrangement or 1,2-migration or 1,2-shift or Whitmore 1,2-shift 1 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. In the example below the substituent R moves from carbon atom C2 to C3.
The rearrangement is intramolecular and the starting compound and reaction product are structural isomers. The 1,2-rearrangement belongs to a broad class of chemical reactions called rearrangement reactions.
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Reaction mechanism
A 1,2-rearrangement is often initialised by the formation of a reactive intermediate such as:
- a carbocation by heterolysis in a nucleophilic rearrangement or anionotropic rearrangement
- a carbanion in a electrophilic rearrangement or cationotropic rearrangement
- a free radical by homolysis
- a nitrene.
The driving force for the actual migration of a substituent in step two of the rearrangement is the formation of a more stable intermediate. For instance a tertiary carbocation is more stable than a secondary carbocation and therefore the SN1 reaction of neopentyl bromide with ethanol yields tert-pentyl ethyl ether.
Carbocation rearrangements are more common than the carbanion or radical counterparts. This observation can be explained on the basis of Hückel's rule. A cyclic carbocationic transition state is aromatic and stabilized because it holds 2 electrons. In an anionic transition state on the other hand 4 electrons are present thus antiaromatic and destabilized. A radical transition state is neither stabilized or destabilized.
The most important carbocation 1,2-shift is the Wagner-Meerwein rearrangement. A carbanionic 1,2-shift is involved in the benzilic acid rearrangement.
Radical 1,2-rearrangements
The first radical 1,2-rearrangement reported by Heinrich Otto Wieland in 1911 2 was the conversion of bis(triphenylmethyl)peroxide 1 to the tetraphenylethane 2.
The reaction proceeds through the triphenylmethoxyl radical A, a rearrangement to diphenylphenoxymethyl C and its dimerization. It is unclear to this day whether in this rearrangement the cyclohexadienyl radical intermediate B is a transition state or a reactive intermediate as it (or any other such species) has thus far eluded detection by ESR spectroscopy 3.
An example of a less common radical 1,2-shift can be found in the gas phase pyrolysis of certain polycyclic aromatic compounds 4. The energy required in an aryl radical for the 1,2-shift can be high (up to 60 kcal/mol or 250 kJ/mol) but much less than that required for a proton abstraction to an aryne (82 kcal/mol or 340 kJ/mol). In alkene radicals proton abstraction to an alkyne is preferred.
1,2 rearrangements
The following mechanisms involve a 1,2-rearrangement:
- Wagner-Meerwein rearrangement
- Pinacol rearrangement
- Hofmann rearrangement
- Curtius rearrangement
- Lossen rearrangement
- SN1 reaction (generally)
- Halogen dance rearrangement
- 1,2-Wittig rearrangement
- Beckmann rearrangement
- Fritsch-Buttenberg-Wiechell rearrangement
- Criegee rearrangement
- Dowd-Beckwith ring expansion reaction
- Brook rearrangement
- Benzilic acid rearrangement
- Favorskii rearrangement
- Wolff rearrangement
- Stevens rearrangement
- Seyferth-Gilbert homologation
- Westphalen-Lettré rearrangement
1,3-Rearrangements
1,3-rearrangements take place over 3 carbon atoms. Examples:
- the Fries rearrangement
- a 1,3-alkyl shift of verbenone to chrysanthenone
References
- ^ Whitmore, Frank C. (1932). "The common basis of molecular rearrangements". J. Am. Chem. Soc. 54 (8): 3274–3283. doi:.
- ^ Wieland, H. Chem. Ber. 1911, 44, 2550-2556.
- ^ Isomerization of Triphenylmethoxyl and 1,1-Diphenylethoxyl Radicals. Revised Assignment of the Electron-Spin Resonance Spectra of Purported Intermediates Formed during the Ceric Ammonium Nitrate Mediated Photooxidation of Aryl Carbinols K. U. Ingold, Manuel Smeu, and Gino A. DiLabio J. Org. Chem.; 2006; 71(26) pp 9906 - 9908; (Note) doi:10.1021/jo061898z
- ^ Brooks, Michele A.; Lawrence T. Scott (1999). "1,2-Shifts of Hydrogen Atoms in Aryl Radicals". J. Am. Chem. Soc. 121 (23): 5444–5449. doi:.
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- This page was last modified on 15 September 2008, at 21:40.
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