1,2-rearrangement

Organic chemical reaction A 1,2-rearrangement or 1,2-migration or 1,2-shift or Whitmore 1,2-shift The common basis of molecular rearrangements Frank C. Whitmore Journal of the American Chemical Society 1932 54 8 3274–3283 10.1021/ja01347a037 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. center|250px|1,2-shift 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. A rearrangement involving a hydrogen atom is called a 1,2-hydride shift. If the substituent being rearranged is an alkyl group, it is named according to the alkyl group's anion: i.e. 1,2-methanide shift, 1,2-ethanide shift, etc. 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 an 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 1911Über Triphenylmethyl-peroxyd. Ein Beitrag zur Chemie der freien Radikale Wieland, H. Chem. Ber. 1911, 44, 2550–2556. 10.1002/cber.19110440380 was the conversion of bis(triphenylmethyl)peroxide 1 to the tetraphenylethane 2. center|400px|Radical 1,2-rearrangement 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.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) 10.1021/jo061898z An example of a less common radical 1,2-shift can be found in the gas phase pyrolysis of certain polycyclic aromatic compounds. 1,2-Shifts of Hydrogen Atoms in Aryl Radicals Michele A. Brooks Lawrence T. Scott Journal of the American Chemical Society 1999 121 23 5444–5449 10.1021/ja984472d 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. center|650px| Aryl radical 1,2-shift in a helicene 1,2-Rearrangements The following mechanisms involve a 1,2-rearrangement: 1,2-Wittig rearrangement Alpha-ketol rearrangement Beckmann rearrangement Benzilic acid rearrangement Brook rearrangement Criegee rearrangement Curtius rearrangement Dowd–Beckwith ring expansion reaction Favorskii rearrangement Friedel–Crafts reaction Fritsch–Buttenberg–Wiechell rearrangement Halogen dance rearrangement Hofmann rearrangement Lossen rearrangement Pinacol rearrangement Seyferth–Gilbert homologation SN1 reaction (generally) Stevens rearrangement Stieglitz rearrangement Wagner–Meerwein rearrangement Westphalen–Lettré rearrangement Wolff rearrangement References Category:Rearrangement reactions