The first application of the Hiyama cross-couplingreaction to the synthesis of retinoids is reported. Oxygen-substituted dienylsilanes (siloxanes, silanols) together with several families of recently described�safety-catch� silanols (i.e. stable precursors that can be unmasked in situ to reveal the reactive silanolitself: siletanes, silyl hydrides, allyl-, benzyl-, aryl-, 2-pyridyl-, and2-thienylsilanes) have been stereoselectively prepared (from an alkyne orhalide precursor), and stereospecifically coupled (upon treatment with apalladium catalyst and a nucleophilic activator) to construct the central C10-C11single bond of the retinoid framework, as the key step. All-trans- and 11-cis-retinoids, and their demethylated analogues in the side chain, havebeen successfully synthesized by this inexpensive, harmless and highlyefficient approach, which establishes a reliable (even superior) alternative tothe traditional Suzuki and Stille protocols.

Hiyama cross-coupling reaction in the stereospecific synthesis of retinoids

239th National Meeting (2010)

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