Title of article :
Synthetic studies on the icetexones: enantioselective formal syntheses of icetexone and epi-icetexone
Author/Authors :
Felipe de Jesus Cortez، نويسنده , , David Lapointe، نويسنده , , Amy M. Hamlin، نويسنده , , Eric M. Simmons، نويسنده , , Richmond Sarpong، نويسنده ,
Issue Information :
هفته نامه با شماره پیاپی سال 2013
Pages :
12
From page :
5665
To page :
5676
Abstract :
Two strategies for the synthesis of the icetexane diterpenoids icetexone and epi-icetexone that rely on Ga(III)-catalyzed cycloisomerization of alkynyl indene substrates to yield fused [6-7-6] tricycles have been explored. In the first approach, access to a tricycle bearing a gem-dimethyl group paved the way for explorations of C–H functionalization of one of the methyl groups in close proximity to a hydroxyl-directing group. This approach was ultimately unsuccessful and led only to ring cleaved products. In the second approach, an alkynyl indene substrate bearing a cyano substituent was utilized, which was effective in providing a functional handle to access the icetexone subclass of diterpenoids. A key epoxide opening/diazene rearrangement sequence was utilized to complete a formal synthesis of icetexone and epi-icetexone, which is discussed in detail. Furthermore, the cyano-containing substrate has been prepared in enantioenriched form using a Rh-catalyzed conjugate addition reaction, which now provides a route to the enantioselective synthesis of these natural products.
Keywords :
Icetexanes , Ga(III) cycloisomerization , Total synthesis , Cycloheptadienes , diterpenes , enantioselective conjugate addition
Journal title :
Tetrahedron
Serial Year :
2013
Journal title :
Tetrahedron
Record number :
1105953
Link To Document :
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