Mechanisms of Brønsted Acid Catalyzed Additions of Phenols and Protected Amines to Olefins: A DFT Study

Authors

  • Xin Li,

    1. Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University Beijing 100871, P. R. China, Fax: +86-010-6275-2612
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  • Siyu Ye,

    1. Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University Beijing 100871, P. R. China, Fax: +86-010-6275-2612
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  • Chuan He,

    1. Department of Chemistry, The University of Chicago 5735 South Ellis Avenue, Chicago, Illinois 60637, USA
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  • Zhi-Xiang Yu

    1. Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University Beijing 100871, P. R. China, Fax: +86-010-6275-2612
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Abstract

DFT calculations at the B3LYP/6-31G(d) level were performed to understand the mechanism of the recentlydeveloped trifluoromethanesulfonic acid (TfOH) catalyzed intermolecular additions of phenols and protected amines to simple olefins. A novel mechanism involving a concerted, eight-membered-ring transition structure for the addition of the alcohol/amine to the alkene with TfOH as a catalyst was located. In the addition transition structure, the alkene substrate is protonated and has significant carbocation character. Calculations to rationalize the relative reactivities of the alcohols and amines, together with the regioselectivity of amide addition to the diene, were also conducted. Factors affecting isomerization of the alkene substrates in the alcohol addition process are discussed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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