The carbon-Ferrier rearrangement: an approach towards the synthesis of C-glycosides

Issue in Honor of Prof Richard R. Schmidt ARKIVOC 2013 (ii) 316-362 The carbon-Ferrier rearrangement: an approach towards the synthesis of C-glycosides Alafia Ali Ansari, Rima Lahiri, and Yashwant D. Vankar* Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208 016, India E-mail: [email protected] This article is respectfully dedicated to Professor Dr. Richard R. Schmidt on the occasion of his 78th birthday Abstract The carbon-Ferrier rearrangement is the reaction of appropriately functionalised glycals, with a variety of carbon nucleophiles such as allyltrimethylsilanes, alkynyltrimethylsilanes, silyl cyanides etc. involving the corresponding nucleophilic addition at the anomeric carbon with concomitant loss of a substituent at C-3. This leads to double bond migration to give 2,3unsaturated sugars which act as useful chiral substrates for further manipulations in organic synthesis. Keywords: Ferrier rearrangement, C-glycosides, unsaturated carbohydrates, allyltrimethylsilanes, alkynylsilanes Table of Contents 1. Introduction 2. Allylic Silanes as Nucleophiles 2.1 Allylsilanes 2.2 Substituted allylsilanes 3. Enol Silyl Ethers as Nucleophiles 4. Organometallic Nucleophiles 5. Propargyl or Alkynyl Silanes 6. Silyl Cyanides 7. Other Nucleophiles 7.1 Silyl ketene acetals 7.2 Aromatic nucleophiles 7.3 Electron-rich nucleophiles 7.4 Olefins Page 316 ©ARKAT-USA, Inc.