TY - JOUR
T1 - Electrophilic aromatic chlorination and haloperoxidation of chloride catalyzed by polyfluorinated alcohols
T2 - A new manifestation of template catalysis
AU - Ben-Daniel, Revital
AU - De Visser, Samuël P.
AU - Shaik, Sason
AU - Neumann, Ronny
PY - 2003/10/8
Y1 - 2003/10/8
N2 - We have demonstrated that a polyfluorinated alcohol, 2,2,2-trifluoroethanol, solvent enables haloperoxidase type activity and the oxychlorination of arenes (benzene and its alkylated derivatives) without a metal catalyst. The polyfluorinated alcohol has a dual function; it catalyzes electrophilic chlorination of less reactive arenes by several orders of magnitude and oxidation of chloride at lower H+ concentrations. DFT calculations show that a complementary charge template in the transition state explains the catalysis of the electrophilic chlorination.
AB - We have demonstrated that a polyfluorinated alcohol, 2,2,2-trifluoroethanol, solvent enables haloperoxidase type activity and the oxychlorination of arenes (benzene and its alkylated derivatives) without a metal catalyst. The polyfluorinated alcohol has a dual function; it catalyzes electrophilic chlorination of less reactive arenes by several orders of magnitude and oxidation of chloride at lower H+ concentrations. DFT calculations show that a complementary charge template in the transition state explains the catalysis of the electrophilic chlorination.
UR - http://www.scopus.com/inward/record.url?scp=0141957601&partnerID=8YFLogxK
U2 - 10.1021/ja0364524
DO - 10.1021/ja0364524
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AN - SCOPUS:0141957601
SN - 0002-7863
VL - 125
SP - 12116
EP - 12117
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 40
ER -