Ylide rearrangements: duality of mechanism in the rearrangement of N-ammonio-amidates

Baldwin, John E.; Brown, James Edward; Cordell, R. W.

doi:10.1039/c29700000031

Cited by 13 publications

(8 citation statements)

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“…109 IIOa, R =CH&H, b, R = CH3 been reported for 1 , l -dimethyl-1 -cinnamylamine-acetimide. 54 Chemical evidence for the free-radical mechanism is the rearrangement of the crotyl, cinnamyl, and y,ydimethylallyl groups without i s~m e r i z a t i o n ,~~ and the trapping of the benzyl group in the rearrangement of 1 , ldimethyl-1 -benzylamine-acetimide and 1,4,4-trimethyl-lbenzyl-3-oxopyrazolinium hydrazide inner salt (1 1 Oa) with benzylthiol and bromotrichloromethane; toluene and benzyl bromide were formed, respectively.l18 This free radical rearrangement is apparently accompanied by a small amount of concerted rearrangement in the pyrolysis of the crotyl derivative. .…”

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confidence: 97%

Chemistry of aminimides

Wawzonek¹

1973

Chem. Rev.

108

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Chemistry of aminimides

Wawzonek¹

1973

Chem. Rev.

108

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“…There has been a long history of attempts to control the [2,3] versus [1,2] selectivity of these reactions. 2 − 5 Reactant structural effects can certainly direct which product is formed. Control of the product for a given reactant of interest is much more difficult.…”

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Controlling Selectivity by Controlling the Path of Trajectories

Biswas

Singleton

2015

J. Am. Chem. Soc.

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Consideration of the role of dynamic trajectories in [1,2]- and [2,3]-sigmatropic rearrangements suggests a counterintuitive approach to controlling the selectivity. In our hypothesis, [2,3] selectivity can be promoted by reaction conditions that thermodynamically disfavor the [2,3] rearrangement step and thereby make the transition state later. The application of this idea has led to a successful prescription for dictating the selectivity in Stevens/Sommelet-Hauser rearrangements of ammonium ylides. A combination of kinetic isotope effects, crossover experiments, and computational dynamic trajectories support the idea that the selectivity is controlled through control of the path of trajectories.

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“…Treatment of olefins with halogens in nitrile solvents leads to -halogenated amides;3 other modifications of the Ritter reaction with 7V,N-dichlorosulfonamides or peracids in nitrile media have also been reported. 4 We wish to report an extension of the Ritter reaction in which the electrophilic reagent is nitronium or nitryl fluoroborate, N02BF4. This salt is known to nitrate and to initiate the polymerization of olefins.…”

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confidence: 99%