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 inChemical communications (Cambridge, England) Vol. 52; no. 66; pp. 10137 - 10140
Main Authors Gan, Zubao, Chu, Zhiwen, Hu, Jia, Su, Zhishan, Hu, Changwei, Gao, Lu, Song, Zhenlei
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 09.08.2016
Subjects
Allyl compounds
Chemical reactions
Chemistry
Chemistry, Multidisciplinary
Chemistry, Pharmaceutical - methods
Derivatives
Esters
Esters - chemistry
Esters - metabolism
Ethers
Ketones - chemistry
Ketones - metabolism
Pathways
Physical Sciences
Science & Technology
Silanes - chemistry
Silanes - metabolism
Tin Compounds - chemistry
Tin Compounds - metabolism
Tuning
ALCOHOLS
ACID
DIELS-ALDER REACTIONS
CYCLIZATION REACTIONS
CHEMISTRY
CARBONYL-COMPOUNDS
AZADIENES
ALDEHYDES
ALLYLSILANES
ALLYLTRIMETHYLSILANE
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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.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
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ISSN:1359-7345
1364-548X
DOI:10.1039/c6cc04593f