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Brønsted Acid Mediated Novel Rearrangements of Diarylvinylidenecyclopropanes and Mechanistic Investigations Based on DFT Calculations
Author(s) -
Li Wei,
Shi Min,
Li Yuxue
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200901172
Subject(s) - brønsted–lowry acid–base theory , chemistry , density functional theory , toluene , reactivity (psychology) , regioselectivity , naphthalene , sulfonic acid , catalysis , lewis acids and bases , solvent , medicinal chemistry , computational chemistry , organic chemistry , medicine , alternative medicine , pathology
Diarylvinylidenecyclopropanes undergo a novel rearrangement in the presence of the Brønsted acid Tf 2 NH (Tf: trifluoromethanesulfonyl) to give the corresponding naphthalene derivatives in good to high yields upon heating, whereas in the presence of the Brønsted acid toluene‐4‐sulfonic acid ( p ‐TSA), the corresponding triene derivatives are afforded in moderate to good yields under mild conditions. Corresponding mechanistic studies on the basis of density functional theory (DFT) with the Gaussian03 program by using the B3LYP method have revealed that the p K a value of the Brønsted acid, as well as the entropy and solvent effects, plays a significant role in this reaction; these factors can discriminate the differences in the reactivity and regioselectivity among the Brønsted acids used in this reaction. In the presence of Lewis acid Sn(OTf) 2 , a butatrienecyclopane can produce the corresponding ring‐opened products in moderate yields.