All together! A unified synthetic strategy has resulted in the first enantioselective total syntheses of the natural products 8‐demethoxyrunanine and cepharatines A, C, and D.
The preparation and synthetic applications of benzoquinone monoketal-derived N-tert-butanesulfinyl imines is described. These synthetically versatile intermediates undergo highly diastereoselective 1,2-addition reactions with organometallic reagents to provide 4-aminocyclohexadienones in good yields. The utility of this methodology is demonstrated in a six-step enantioselective synthesis of (-)-3-demethoxyerythratidinone.
Synthetic efforts toward the chlorinated propellane alkaloid acutumine (1) are described. The key vicinal quaternary centers were constructed by a photochemical [2+2] cycloaddition reaction of a furanyl-tetrahydroindolone. Dihydroxylation of the [2+2] product enabled a tandem retro-aldol/intramolecular ketalization reaction, which revealed the aza-propellane core of 1 while generating an unusual, caged, pentacyclic hemi-ketal product.
Alle gemeinsam! Eine vereinheitlichte Synthesestrategie ermöglichte die erste enantioselektive Totalsynthese der Naturstoffe 8‐Demethoxyrunanin, Cepharatin A, Cepharatin C und Cepharatin D.
An enantioselective synthesis of (À )-10hydroxyacutuminine is reported. Central to our strategy is a photochemical [2+2] cycloaddition that forges two of the quaternary stereocenters present in the acutumine alkaloids. A subsequent retro-aldol/Dieckmann sequence furnishes the spirocyclic cyclopentenone. Efforts to chlorinate the acutumine scaffold at C10 under heterolytic or radical deoxychlorination conditions led to the synthesis of an unexpected cyclopropane-containing pentacycle.
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