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Double inversion of the secondary nitrogens in cis-Diaziridinocyclopentane

✍ Scribed by Michał W. Majchrzak; Antoni Kotełko; Joseph B. Lambert

Publisher
John Wiley and Sons
Year
1983
Tongue
English
Weight
427 KB
Volume
21
Category
Article
ISSN
0749-1581

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✦ Synopsis

l~~4cu,~-3,7-Diazatricyelo[4.1.0.0~4]heptane (cis-diaziridinocyclopentane) (1) has been prepared from the analogous cis-diepoxycyclopentane. Ring opening of the diepoxide with sodium azide produced a pair of regioisomeric azido alcohols. Tosylation and treatment with lithium aluminum hydride produced 1 . The dibenzoyl derivative possessed the di-ex0 stereochemistry for the tertiary &dine nitrogem. The 'H spectrum of 1 was temperature dependent. Both the CH and NH resonances underwent decoalescence as the temperature was lowered. Because the rate was independent of concentration, the mechanism is probably inversion of the secondary nitrogen, the first such example to occur by the interchange of two diastereotopic, secondary 0 amine nitrogens within the same molecule. The free energy of activation at coalescence (0 "C) was measured to be 12.8 kcal mol-l. The unsymmetrical slow exchange of 1 is clearly consistent with the exo,endo stereochemistry for the secondary azmdine nitrogem, possibly stabilized by intramolecular attraction.

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