The regioselectivity of the reductive cleavage of 3,4,5-trimethoxybenzyl methyl ether strongly depends on the alkali metal employed as a reducing agent and solvent effects. Reactions run using Na as a reducing agent led to aromatic C(4)-O bond cleavage, whilst reductions run in the presence of Na/15-crown-5, or using Li as a reducing agent, led to highly regioselective benzylic C-O bond cleavage. This regioselectivity turnaround is discussed in terms of major solvent effects affecting the fragmentation paths of a common reaction intermediate. Synthetic applications of these findings led to the synthesis of biologically active compounds, like 2,5-dialkyl-substituted resorcinols, or 1-(3,4,5-trimethoxyphenyl)-2-arylethanes structurally related to combretastatin. (C) 2007 Elsevier Ltd. All rights reserved
Ion Pairing Effects on the Regioselectivity of Arylic vs. Benzylic C-O Bond Reductive Cleavage: Synthetic Applications / Azzena, Ugo Gavino; Dettori, G.; Mascia, I.; Pisano, Luisa; Pittalis, M.. - In: TETRAHEDRON. - ISSN 0040-4020. - 63:(2007), pp. 11998-12006. [10.1016/j.tet.2007.09.010]
Ion Pairing Effects on the Regioselectivity of Arylic vs. Benzylic C-O Bond Reductive Cleavage: Synthetic Applications
AZZENA, Ugo Gavino;PISANO, Luisa;
2007-01-01
Abstract
The regioselectivity of the reductive cleavage of 3,4,5-trimethoxybenzyl methyl ether strongly depends on the alkali metal employed as a reducing agent and solvent effects. Reactions run using Na as a reducing agent led to aromatic C(4)-O bond cleavage, whilst reductions run in the presence of Na/15-crown-5, or using Li as a reducing agent, led to highly regioselective benzylic C-O bond cleavage. This regioselectivity turnaround is discussed in terms of major solvent effects affecting the fragmentation paths of a common reaction intermediate. Synthetic applications of these findings led to the synthesis of biologically active compounds, like 2,5-dialkyl-substituted resorcinols, or 1-(3,4,5-trimethoxyphenyl)-2-arylethanes structurally related to combretastatin. (C) 2007 Elsevier Ltd. All rights reservedI documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
