Tunable reactivity of geminal bis(silyl) enol derivatives leading to selective exo-IEDDA or Sakurai allylation with a beta,gamma-unsaturated ketoester
Two contrasting pathways in a SnCl4-catalyzed reaction of geminal bis(silyl) enol derivatives with beta,gamma-unsaturated ketoesters have been achieved by tuning the R group in the enol moiety. While the electron-donating Bn-substituted enol ether undergoes an exo-selective inverse-electron-demand D...
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Published in | Chemical communications (Cambridge, England) Vol. 52; no. 66; pp. 10137 - 10140 |
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Main Authors | , , , , , , |
Format | Journal Article |
Language | English |
Published |
CAMBRIDGE
Royal Soc Chemistry
09.08.2016
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Subjects | |
Online Access | Get full text |
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Summary: | Two contrasting pathways in a SnCl4-catalyzed reaction of geminal bis(silyl) enol derivatives with beta,gamma-unsaturated ketoesters have been achieved by tuning the R group in the enol moiety. While the electron-donating Bn-substituted enol ether undergoes an exo-selective inverse-electron-demand Diels-Alder (IEDDA) reaction to give dihydropyran, the electron-withdrawing Ac-substituted enol ester reacts as an allylsilane to provide a Sakurai-allylated product with predominant syn-selectivity. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 1359-7345 1364-548X |
DOI: | 10.1039/c6cc04593f |