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Issue 19, 2014
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Regioselective 1,4- over 1,2-addition of 3,3-bis(silyl) allyloxy lithium to enals, enones and enoates. The remarkable α-effect of silicon

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Abstract

A remarkable α-effect of silicon has been discovered that results in soft nucleophilicity at the Cγ of 3,3-bis(silyl) allyloxy lithium 1. The addition of 1 to α,β-unsaturated carbonyl compounds, including enals, proceeds in a 1,4- over 1,2-manner with medium to good regioselectivity, whereas the parent allyloxy lithium 4 undergoes complete 1,2-addition. The results from DFT calculations of HMPA-complexed 1 and 4 provide the rationale to explain this different regioselectivity.

Graphical abstract: Regioselective 1,4- over 1,2-addition of 3,3-bis(silyl) allyloxy lithium to enals, enones and enoates. The remarkable α-effect of silicon

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Publication details

The article was received on 19 Jan 2014, accepted on 06 Mar 2014 and first published on 06 Mar 2014


Article type: Communication
DOI: 10.1039/C4OB00139G
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Org. Biomol. Chem., 2014,12, 3021-3025

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    Regioselective 1,4- over 1,2-addition of 3,3-bis(silyl) allyloxy lithium to enals, enones and enoates. The remarkable α-effect of silicon

    X. Ye, X. Sun, Z. Huang, N. Yang, Z. Su, C. Hu and Z. Song, Org. Biomol. Chem., 2014, 12, 3021
    DOI: 10.1039/C4OB00139G

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