Preparation and evaluation of nitrene precursors (PhI=NSO2Ar) for the copper-catalyzed aziridination of olefins

Tetrahedron Letters

Volumn 38, Issue 39, 1997, Pages 6897-6900

  Södergren, Mikael J ^a   Alonso, Diego A ^a   Bedekar, Ashutosh V ^a   Andersson, Pher G ^a  

^a UPPSALA UNIVERSITY   (Sweden)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; AZIRIDINE; AZIRIDINE DERIVATIVE; COPPER; REAGENT;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; PRECURSOR; REACTION ANALYSIS;

EID: 0037782375     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)01589-X     Document Type: Article

References (23)

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18. 5 in that no water was added after the reaction was complete, but the crude products were collected directly by filtration, dried in vacua and used in the aziridination reactions. Furthermore, the solvent volume used for the preparation of 1c was only half of that employed in the original procedure.
19. 2N=IPh for rhodium-catalyzed aziridination of olefins, see Müller, P.; Baud, C.; Jacquier, Y. Tetrahedron 1996, 52, 1543.
20. 2N=IPh (1e) show that the rate of aziridine formation is significantly faster when 1c serves as the nitrenoid source, while the use of 1e results in a considerably slower reaction. The observation that 1c and 1e give higher chemical yields than 1b in all the cases so far observed may be rationalized in terms of differences in the relative kinetics of the two competing reaction pathways from the copper-nitrene complex, i.e. aziridine versus sulfonamide formation.4b We speculate that the higher yields obtained with 1c and 1e might be due to higher reactivity of 1c and slower decomposition of 1e.
21. Södergren, M. J.; Bedekar, A. V.; Alonso, D. A.; Andersson P. G. unpublished results.
22. 4 (16 mg, 0.05 mmol) are dissolved in dry acetonitrile (2.5 mL) containing activated 4A molecular sieves (ca 300 mg). 1e (610 mg, 1.5 mmol) is added portionwise under argon over a period of three hours. The reaction mixture was then stirred overnight, followed by evaporation of the solvent under reduced pressure. The residue was directly subjected to flash chromatography (silica gel, Pentane/EtOAc: 85/15) to afford aziridine 2a (301 mg, 99%) as a white solid.
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