Both symmetrical and nonsymmetrical trans-2,3-diaryloxiranes are regio- and stereoselectively opened by the LiBr/Amberlyst 15 system. In the case of symmetrical trans-stilbene oxide, the synversus anti-bromohydrins ratio ranged between 88/12 and 30/70, by varying the reaction temperature from 20 to -30 °C. In the case of nonsymmetrical para-substituted trans-2,3-diaryloxiranes, the regioselectivity is determined by electronic effects. If one phenyl bears a strong electronwithdrawing group (as NO2 or CF3), the nucleophilic attack is totally on the beta-carbon with respect to the substituted phenyl ring. With one phenyl bearing a strong electron-releasing group (OCH3), the regioselectivity is reversed. Ab initio calculation at the DFT/B3LYP/6-31G* level, run on protonated epoxide structures, supports the formation of a cationic acyclic intermediate. Application of the method on ortho-methoxy and ortho-nitro 2,3-diaryloxiranes afforded the syn-bromohydrins in excellent yield, via regio- and stereoselective opening at either alpha- or beta-carbon, respectively.

Regio and stereoselective oxiranyl ring opening of 2,3-diaryl oxiranes by LiBr/Amberlyst 15: a new stereocontrolled access to 1,2 diaryl-2-bromoalcohols

BONINI, Carlo Cesare;LUPATTELLI, Paolo
2005

Abstract

Both symmetrical and nonsymmetrical trans-2,3-diaryloxiranes are regio- and stereoselectively opened by the LiBr/Amberlyst 15 system. In the case of symmetrical trans-stilbene oxide, the synversus anti-bromohydrins ratio ranged between 88/12 and 30/70, by varying the reaction temperature from 20 to -30 °C. In the case of nonsymmetrical para-substituted trans-2,3-diaryloxiranes, the regioselectivity is determined by electronic effects. If one phenyl bears a strong electronwithdrawing group (as NO2 or CF3), the nucleophilic attack is totally on the beta-carbon with respect to the substituted phenyl ring. With one phenyl bearing a strong electron-releasing group (OCH3), the regioselectivity is reversed. Ab initio calculation at the DFT/B3LYP/6-31G* level, run on protonated epoxide structures, supports the formation of a cationic acyclic intermediate. Application of the method on ortho-methoxy and ortho-nitro 2,3-diaryloxiranes afforded the syn-bromohydrins in excellent yield, via regio- and stereoselective opening at either alpha- or beta-carbon, respectively.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/1653070
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