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Progress in Chemistry 2011, Vol. 23 Issue (01): 165-180 Previous Articles   Next Articles

• Review •

Regioselective Nucleophilic Ring Opening Reactions of Unsymmetric Oxiranes

Zhou Chan, Xu Jiaxi   

  1. State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, Faculty of Science, Beijing University of Chemical Technology, Beijing 100029, China
  • Received: Revised: Online: Published:
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Nucleophilic ring opening reactions of unsymmetric oxiranes and their regioselectivity with widely used nucleophiles are reviewed. Strong nucleophiles attack the less substituted carbon atom of unsymmetric oxiranes, whatever alkyl, alkenyl, and aryloxiranes, controlled by the steric hindrance only. They can undergo an SN2' ring-opening reaction with alkenyloxiranes via the attack on the β-carbon atom of their alkenyl group. Other nucleophiles generally attack the less substituted carbon atom for alkyloxiranes, controlled by the steric hindrance, but attack the arylmethyl and allyl carbon atom for aryl and alkenyloxiranes, controlled by the electronic effect. In the presence of proton acids or strong Lewis acids, although monoalkyloxiranes are attacked on their less substituted carbon atom with nucleophiles (steric hindrance control), aryl, alkenyl, and geminal dialkyloxiranes are attacked on their more substituted carbon atom with weak nucleophiles (electronic effect control). The regioselectivity of intramolecular nucleophilic ring opening reaction of oxiranes is controlled by the ring size of products. The favorable order is five-membered ring > six-membered ring > seven-membered ring. Thus, the regioselectivity is controlled by a balance between the steric hindrance and electronic effect of oxiranes and nucleophiles.

Key words: oxirane, nucleophile, nucleophilic ring opening reaction, regioselectivity

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