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Progress in Chemistry 2004, Vol. 16 Issue (02): 220- Previous Articles   Next Articles

• Review •

Nucleophilic Ring Opening Reaction of Unsymmetric Aziridines and Its Regioselectivity

Ma Linge;Xu Jiaxi**   

  1. (Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Department of Chemical Biology, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China)
  • Received: Revised: Online: Published:
  • Contact: Xu Jiaxi
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Nucleophilic ring opening reaction of unsymmetric aziridines and its regioselectivity with various nucleo-philes was reviewed systematically. The regioselectivity is controlled by a balance between steric hindrance and electronic effect in an aziridine ring. Nucleophilic ring opening reaction of non-aryl and non-alkenyl substituted aziridines occurs generally on the less substituted carbon atom in their aziridine rings, controlled by steric hindrance. However, ihe reaction of aiyl and alkenyl substituted aziridines does on arylmethyl and allyl carbon atom, controlled by electronic effect, and the reaction of alkenyl substituted aziridines can also occur on the /3-carbon atom of the alkenyl group. The regiose-lectivity of intramolecular nucleophilic ring opening reaction of aziridines is controlled by the ring size of products, five-membered ring > six-membered ring > seven-membered ring. For a nucleophile, its regioselectivity is also controlled by both steric hindrance and electronic effect. However, a stronger nucleophile is generally just controlled by steric hin-drance. A nucleophile which prefers to form a stable free radical undergoes a single electron transfer mechanism in ring opening reaction of aziridines to generate products which could be obtained via its attacking on more substituted carbon at-om in an aziridine ring.
Key words: aziridine, nucleophile, nucleophilic ring opening reaction, regioselectivity

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