Synthesis of Hirsutene by Curran

28 Setembro 2016, 14:00 Christopher David Maycock

A synthesis of Hirsutene is described. Racemic synthesis with stereo control

Strategy based upon radical cyclisation.
Synthesis of radical precursor.
Selection of starting material.
1,2- or 1,4-addition in cyclopentenones. Use of Ce(III) reagents for selective 1.2 reduction. Formation of esters using activated carboxylic acids. Equilibrium and reaction conditions (reagents). Carbon acids and the use of strong non-nucleophilic bases (LDA). Formation of enolsilyl ethers and the chemistry of some silicon compounds. Cope rearrangement and the formation of C-C bonds. Selenolactonisation: stereochemistry and utility.
Oxidation of sulfur and selenium to sulfoxides and selenoxides. Pericyclic reaction of selenoxides and 2,3-sigmatropic rearrangements and the formation of double bonds. The THP protecting group. Formation of organolithium reagents by Br-Li exchange. Conversion to copper reagents and their use in 1,4-additions to nones and SN2' reactions.