Tunable reactivity of geminal bis(silyl) enol derivatives leading to selective exo-IEDDA or Sakurai allylation with a beta,gamma-unsaturated ketoester

• Published in: Chemical 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
• Language: English
• 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

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...