Migration label

Roberts seems to have been the first to propose the existence of a carbonium ion intermediate with a bridging methyl group (a structure that we would now call a corner-protonated cyclopropane), in part as a result of a study on the deamination of propylamine-1-in an aqueous medium, in which it was believed that a small amount of label migration to both C(2) and C(3) of the 1-propanol product was observed (Figure 50). In fact, the analysis of the label position was later shown to be in error but, by then, other experiments had suggested the existence of some kind of protonated cyclopropane. Among these were studies showing the formation of cyclopropanes from deamination of alkylamines in non-aqueous media. This process was subjected to further scrutiny... 

Localization of isotopes possible partial labelling migration, but possible... 

Pyrimidylnitrenes (313) undergo ring contraction after rearrangement, as shown by the complete label migration. In this case the products are 1-cyanoimidazoles (316) (contrast to the pyridylnitrenes), and the yields are... 

The label migration, observed only in the product from the gas-phase decay, provides the first ecperimental evidence for a degenerate rearrangement of the gaseous phenylium cation. 

The rearrangement of the ion (96) into the ion (97) must nevertheless, just like other isomeric conversions of arenium ions, be reversible. This is indirectly indicated by the label migration over the ring in 2,3,4,4,5,6-hexamethylcyclohexa-2,5-dienone-1- C when heated with the (CHaj O BF3 complex These date and those on the isomeric conversions of phenylpentamethylbenzenium ions indicate that the migrating group may also appear at the carbon bonded with oxygen. 

Fragment A photolabeled in the pesence of [carbonyl- ClNAD was digested with cyanogen bromide, and the products were fractionated on Sephadex G-75. Most of the label migrated with a single peak (of four). This peak contained peptide CNBr-3, which corresponded to residues 116-178 of fragment A. 

Below — 140°C, the EPR spectrum observed was that of the cyclopropylmethyl radical. If the photolysis was done above — 140°C, however, the spectmm of a second species was seen, and above — 100°C, this was the only spectmm observed. This second spectmm could be shown to be that of the 3-butenyl radical. This study also established that the 3-butenyl radical did not revert to the cyclopropylmethyl radical on being cooled back to — 140°C. The conclusion is that the ring opening of the cyclopropyl radical is a very facile process and that the lifetime of the cyclopropyl radical above — 100°C is very short. Even though the equilibrium favors the 3-butenyl radical, the reversible ring closure can be detected by isotopic labeling experiments, which reveal the occurrence of deuterium migration ... 

Terminally deuterium-labeled phenylacetylene was also used to elucidate the possible mechanism of this reaction. In view of all these results, a rationalization for the loss of the trimethylsilyl and the migration of the ethoxy group from its original position in the complex 96 has been put forward. Due to the contribution of the conjugated diarylcyclopentadiene moiety in 98 and 99, these molecules showed intense fluorescence with a relatively high quantum yield of 46%. 

The thiazolecarboxylic acid structure (40) was also guessed in a similar way, from tracer experiments. The unknown compound was converted into the thiamine thiazole by heating at 100°C and pH 2. On paper electrophoresis, it migrated as an anion at pH 4. Tracer experiments indicated that it incorporated C-l and C-2 of L-tyrosine, and the sulfur of sulfate. The synthetic acid was prepared by carboxylation of the lithium derivative of the thiamine thiazole, and the derivatives shown in Scheme 19 were obtained by conventional methods. Again, the radioactivity of the unknown, labeled with 35S could not be separated from structure 40, added as carrier, and the molar radioactivity remained constant through several recrystallizations and the derivatizations of Scheme 17. 

With 6-alkenoic acids the intermediate radical partially cyclizes to a cyclopentyl-methyl radical in a 5-exo-trig cycHzation [139] (Eq. 6) [138 a, 140] (see also chap. 6). To prevent double bond migration with enoic acids the electrolyte has to be hindered to become alkaline by using a mercury cathode. Z-4-Enoic acids partially isomerize to -configurated products. Results from methyl and deuterium labelled carboxylic acids support an isomerization by way of a reversible ring closure to cyclopropyl-carbinyl radicals. The double bonds of Z-N-enoic acids with N > 5 fully retain their configuration [140]. 

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. 

A 1,2-shift has been observed in radicals bearing an OCOR group at the p-carbon where the oxygen group migrates as shown in the interconversion of 36 and 37. This has been proven by isotopic labeling experiments and other mechanistic explorations. A similar rearrangement was observed with phosphatoxy alkyl radicals such as 38. ... 

However, 1,2 migration of alkyl groups has been shown to occur in certain diradicalsFor example, the following rearrangement has been established by tritium labeling. 

If the reaction is carried out with ketone labeled in the C=0 group with the first pathway predicts that the product will contain all the " C in the C=0 carbon, while in the second pathway the label will be in the a carbon (demonstrating migration of oxygen). The results of such experiments have shown that in some cases only the C=0 carbon was labeled, in other cases only the a carbon, while in still others both carbons bore the label, indicating that in these cases both pathways were in operation. With a-hydroxy aldehydes and ketones, the process may stop after only one migration (this is called the a-ketol rearrangement). 

The fact that C-1 and C-2 were found to be equally labeled showed that both migrations occurred, with equal probability. Since C-2 and C-6 of 58 are not... 

Evidence for migration of the arylthio group across the double bond comes from C-14 labeling studies on ester 213 and product studies from unsymmetrical vinyl sulfonates 214 (181). Complete scrambling of the C-14... 

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