Stereochemistry of the Deamination of Aziridines<sup>1a,b</sup>

Clark, Ronald D.; Helmkamp, George K.

doi:10.1021/jo01029a011

Cited by 65 publications

(21 citation statements)

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“…The primary isomerization processes which have been noted are of three types (223) - (225). Such molecules may exist in three forms, differing in the number of x electrons occupying the allyl orbital.…”

Section: Angewmentioning

confidence: 99%

The Conservation of Orbital Symmetry

Woodward

Hoffmann

1969

Angew. Chem. Int. Ed. Engl.

2,930

1,786

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Section: Angewmentioning

confidence: 99%

The Conservation of Orbital Symmetry

Woodward

Hoffmann

1969

Angew. Chem. Int. Ed. Engl.

2,930

1,786

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“…TS1 eliminates one molecule of HCl to form N‐nitrosoaziridine (A4). The formation of N‐nitrosoaziridine and HCl has been confirmed experimentally 4. The HCl formed has been reported to form aziridine hydrochloride, and N‐nitrosoaziridine has been isolated as a yellow oil at low temperature and has been found to be stable at low temperatures.…”

Section: Resultsmentioning

confidence: 74%

“…Aziridines can be deaminated by nitrosating it with nitrosyl chloride or nitromethane or 3‐nitro‐N‐nitrosocarbazole and denitrosating it. In the reaction with NOCl the alkene produced is 99% cis deaminated 1, 4. Clark and Helmkamp 4 studied the deamination of stereoisomers of 2,3‐dimethylaziridines by NOCl and the products obtained were found to be completely stereospecific.…”

Section: Introductionmentioning

confidence: 99%

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Ab initio and DFT modeling of stereoselective deamination of aziridines by nitrosyl chloride

Kalaiselvan¹,

Venuvanalingam²,

Poater³

et al. 2004

Int J of Quantum Chemistry

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ABSTRACT:The stereochemical course of the deamination of cis-2,3-dimethylaziridine by nitrosyl chloride was investigated at the QCISD/6-31G(d) level. Calculations reveal that the reaction takes place in two steps. In the first step, the reactants form a pre-reactive complex, followed by a spiro-type bicyclic transition state, which on dissociative cycloelimination gives the N-nitrosoaziridine intermediate. In the second step, this intermediate undergoes cycloreversion through a slightly asynchronous concerted transition state to form an alkene with the same stereochemistry, which is in total agreement with experiment. In the whole reaction, the denitrosation step is found to be rate-determining. For comparison, geometry optimizations and energies were also obtained at the B3LYP/6-31G (d) contribution of exact exchange in the Becke functional. With respect to the QCISD results, it has been shown that the functional with 0% exact exchange yields the best activation barriers, whereas the functional with 30% exact exchange is the most suitable one to carry out the complexation and reaction energy calculations.

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“…Group VA (N,P,As). The reaction of aziridines with nitrosyl chloride (276,277) and other nitrosating reagents such as HNO 2 , C 4 H 9 ONO, or NOBF 4 (18) proceeds via the thermally unstable N-nitrosoaziridines and leads to deamination. Coupling of aromatic diazonium salts with aziridines gives 1-arylazoaziridines, many of which are explosive.…”

Section: Reaction With Further Electrophiles Of Group Ivamentioning

confidence: 99%