Migrations, intramolecular

Rearrangement (Section 5.13) Intramolecular migration of an atom, a group, or a bond from one atom to another. 

The ab initio calculated 1,2-H intramolecular migration in azoles has a barrier of 50 kcal... 

There is evidence from labeling that intramolecular migration occurs only through 1,2 shifts. Any 1,3 or 1,4 migration takes place by a series of two or more 1,2 shifts. 

Eairley DJ, DR Boyd, ND Sharma, CCR Allen, P Morgan, MJ Larkin (2002) Aerobic metabolism of 4-hydroxybenzoic acid in Archaea via an unusual pathway involving an intramolecular migration (NIH shift). Appl Environ Microbiol 68 6246-6255. 

An n.m.r. study of the permutational isomerisations within a series of amidium fluorophosphates (133) has revealed an irregular mechanism with dissociation of the P-N and also the P-0 bonds of the bidentate ligands and the formation of five-coordinate intermediates (134)61. Reversible intramolecular migrations of pentaco-ordinate phosphorus in the N-C-N triad of amidines (e.g. 135, 136,... 

Carbohydrate chemistry contains many examples of intramolecular migration of substituent groups. The largest number of these involve acyl groups, but migrations in phosphoric esters, and certain ethers have also been reported. Surprisingly, the topic has not been the subject of a comprehensive review, but there are several useful summaries thereof.539-542 In this Section, mainly those examples that have... 

The formation of acetaldehyde from the w-olefin complex was shown to involve intramolecular migration of a hydrogen atom from one carbon of the ethylene to the other, rather than 0H attack on a vinyl group generated by hydride abstraction with Pd (CH2=CH+ + OH -> CH2=CH0H) followed by rearrangement of the vinyl alcohol to acetaldehyde, since hydrolysis in DgO yielded acetaldehyde free of deuterium (59). 

The effect of temperature on the reduction of nitro-alkanes has been extensively exploited in the synthesis of cp-ephedrine analogues [i5,21,22] starting from 1-aryl-2-nitropropenes which are easily converted to the substrates 2. Reduction of these nitrocompounds below 20° C affords the hydroxylamine. The amine is formed above 55° C. Neutralisation of either reaction mixture causes rapid intramolecular migration of the acetyl group from oxygen to nitrogen, a reaction which implies a... 

The complex, XLYI, may add to another molecule of isobutylene to yield a higher polymer complex or eliminate aluminum chloride to yield the dimer in the latter case intramolecular migration (a 1,5-shift 1) of hydrogen must be postulated in order to form an olefin. On the other hand, cyclization may readily occur (particularly after a 1,2-shift of a proton from a methyl group) with the resultant formation of a naphthene. 

The very high value of Cm for vinyl chloride is attributed to a reaction sequence involving the propagating center XVIII formed by head-to-head addition [Hjertberg and Sorvik, 1983 Llauro-Darricades et al., 1989 Starnes, 1985 Starnes et al., 1983 Tornell, 1988]. Intramolecular migration of a chlorine atom (Eq. 3-114) yields the secondary radical XIX that subsequently transfers the chlorine atom to monomer (Eq. 3-115) to yield poly(vinyl chloride)... 

This hydroxylation-induced intramolecular migration, known as the NIH shift, was explained by the involvement of arene oxides formed by the attack of electrophilic oxoiron(V) porphyrin on the aromatic ring.753 Intermediate 98 was also suggested to be formed in hydroxylation by the Fenton and related reagents in aprotic media after initial oxidation with an oxoiron(V) complex followed by electron transfer.744 754... 

The detection of minor amounts of monobenzyl phosphate, which presumably arise from hydrolysis of the monobenzyl acyl phosphate, is an example of the intramolecular migration of monoalkyl hydrogen phosphate. This process resembles the acid-catalyzed migration of a phosphoryl moiety adjacent to a vicinal hydroxyl function128-130, viz. 

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