Ketyl Radical Cyclization of β-Disubstituted Acrylates: Formal Syntheses of (+)-Secosyrin 1 and Longianone and the Total Synthesis of (+)-4-epi-Secosyrin 1

Citations Over TimeTop 17% of 2013 papers

Abstract

A novel approach to the synthesis of a series of 1,7-dioxaspirononanes that applies a ketyl radical cyclization strategy is described. Radical cyclization of the β-disubstituted acrylate 23, prepared in five steps from (R)-1,2-isopropylideneglycerol, gives both 2,3-syn- and 2,3-anti-furan products. The densely functionalized furan heterocycles are used to complete a concise formal synthesis of secosyrin 1, a metabolite of Pseudomonas syringae, and the total synthesis of 4-epi-secosyrin 1.

Related Papers

• → Cp2TiPh-coordinated cyano and ester groups as efficient ketyl radical acceptors in the reductive radical cyclization of γ- and δ-cyano ketones and δ-keto esters(1998)33 cited
• → Radical Additions to (η6‐Arene)(tricarbonyl)‐chromium Complexes: Diastereoselective Synthesis of Hydrophenalene and Hydrobenzindene Derivatives by Samarium(II) Iodide Induced Cyclization(1995)104 cited
• → Ketyl Radical Cyclization of β-Disubstituted Acrylates: Formal Syntheses of (+)-Secosyrin 1 and Longianone and the Total Synthesis of (+)-4-epi-Secosyrin 1(2013)10 cited
• → Formal Synthesis of FPA, a Kainoid Amino Acid, via Ketyl Radical Cyclization(2002)11 cited
• → Protecting Group Free Formal Total Synthesis of the Antitubercular Agent Erogorgiaene(2012)2 cited