title: Tunable reactivity of geminal bis(silyl) enol derivatives leading to selective exo-IEDDA or Sakurai allylation with a β,γ-unsaturated ketoester.
abstract: Two contrasting pathways in a SnCl4-catalyzed reaction of geminal bis(silyl) enol derivatives with β,γ-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.
authors.affiliation: Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry, West China School of Pharmacy, Sichuan University, Chengdu, 610041, China. zhenleisong@scu.edu.cn.
authors.forename: Zubao
authors.initials: Z
authors.lastname: Gan
authors.affiliation: Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry, West China School of Pharmacy, Sichuan University, Chengdu, 610041, China. zhenleisong@scu.edu.cn.
authors.forename: Zhiwen
authors.initials: Z
authors.lastname: Chu
authors.affiliation: Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry, West China School of Pharmacy, Sichuan University, Chengdu, 610041, China. zhenleisong@scu.edu.cn.
authors.forename: Jia
authors.initials: J
authors.lastname: Hu
authors.affiliation: Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, P. R. China.
authors.forename: Zhishan
authors.initials: Z
authors.lastname: Su
authors.affiliation: Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, P. R. China.
authors.forename: Changwei
authors.initials: C
authors.lastname: Hu
authors.affiliation: Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry, West China School of Pharmacy, Sichuan University, Chengdu, 610041, China. zhenleisong@scu.edu.cn.
authors.forename: Lu
authors.initials: L
authors.lastname: Gao
authors.affiliation: Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry, West China School of Pharmacy, Sichuan University, Chengdu, 610041, China. zhenleisong@scu.edu.cn and State Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu, 610041, China.
authors.forename: Zhenlei
authors.initials: Z
authors.lastname: Song
mesh_terms: D002626:Chemistry, Pharmaceutical / Q000379:methods*; D004952:Esters / Q000737:chemistry* / Q000378:metabolism; D007659:Ketones / Q000737:chemistry / Q000378:metabolism; D012821:Silanes / Q000737:chemistry* / Q000378:metabolism; D017971:Tin Compounds / Q000737:chemistry* / Q000378:metabolism
chemical_list: D004952:Esters; D007659:Ketones; D012821:Silanes; D017971:Tin Compounds; C041694:stannic chloride