No abstract

Intramolecular Kharasch-type additions of trichloroacetamides on anisole and enol acetates catalyzed by Grubbs' ruthenium carbenes are described. This protocol provides access to highly functionalized 2-azaspiro[4.5]decanes, morphan compounds, and the azatricyclic core of FR901483.

A novel synthetic entry to 2-azabicyclo[3.3.1]nonanes based on a copper(I)-catalyzed intramolecular coupling of amino-tethered trichloroacetamides and unsaturated nitriles, esters and alkenes, as well as enol acetates, is described. A study of the reaction conditions and the scope of the process is reported.

The CuI‐mediated atom transfer radical cyclization of amino‐tethered dichloromalonamides and electron‐rich, electron‐poor, and nonactivated double bonds is a useful methodology for the synthesis of 2‐azabicyclo[3.3.1]nonanes. A study of the reaction conditions and the scope of the process is reported. Cyclopropane ring formation was observed from the resulting 1,3‐dichlorides in some morphan substrates using either CuI, Pd, or Zn.

Synthesis of the tetracyclic cores of madangamines D-F was achieved, featuring a reductive radical process from an ethoxycarbonyldichloroacetamide to build the morphan nucleus, a Mitsunobu-type aminocyclization toward the common diazatricyclic intermediate, and ring-closing metathesis reactions for the macrocyclization step leading to the 13- to 15-membered rings.