1,2-rearrangement

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A 1,2-rearrangement 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 C1 to C2.

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.

Reaction mechanism

A 1,2-rearrangement is often initialised by the formation of a reactive intermediate such as:

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/mole). In alkene radicals proton abstraction to an alkyne is preferred.

1,2 Rearrangements

The following mechanisms involve a 1,2-rearrangement:

1,3-Rearrangements

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

References

  1. Whitmore, Frank C. (1932). "The common basis of molecular rearrangements". J. Am. Chem. Soc. 54 (8): 3274–3283. doi:10.1021/ja01347a037. 
  2. Wieland, H. Chem. Ber. 1911, 44, 2550-2556.
  3. 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
  4. Brooks, Michele A. (1999). "1,2-Shifts of Hydrogen Atoms in Aryl Radicals". J. Am. Chem. Soc. 121 (23): 5444–5449. doi:10.1021/ja984472d.  Unknown parameter |coauthors= ignored (help)

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