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| - Convergent Stereocontrol in Peterson Olefinations. Application tothe Synthesis of (±)-3-Hydroxybakuchiol and Corylifolin
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| - The iron-catalyzed Kirmse reaction was used to generate neopentyl α-silyl thioethers that wereelaborated to meroterpenes using two complementary routes: one route involved a sila-Pummererrearrangement, and the other route involved a Peterson olefination. While severe eclipsinginteractions undermined the efficiency of the stereospecific sila-Pummerer rearrangement, theymade it possible to stereoselectively generate E olefins without isolation or separation of syn- andanti-β-silyl alkoxides. Addition of a neopentyl α-silyl alkyllithium intermediate to an aryl aldehydegenerated a mixture of syn- and anti-β-silyl alkoxides. The syn-β-silyl alkoxide eliminatedstereospecifically at −78 °C to give an E olefin, whereas the anti-β-silyl alkoxide was unreactive.The reaction mixture was then acidified and heated to induce stereospecific elimination of the antiisomer to give the same E olefin via a complementary cationic pathway. This route was used tocomplete the first synthesis of the meroterpene (±)-3-hydroxybakuchiol. In addition, we synthesizedanother meroterpene corresponding to the natural product corylifolin and offer evidence that thestructure of corylifolin was misassigned.
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