Hiyama Cross-Coupling Reaction in the Stereospecific Synthesis of Retinoids

The first application of the Hiyama reaction to the synthesis of retinoids is reported. A range of organosilicon moieties (slioxanes, silanols and three kinds of safety-catch silanols) were successfully coupled, under activation, to obtain trans-retinol or 11-cis-retinol with high yield and stereoselectivity. The advantageous properties of the silicon-based coupling partners and the mild reaction conditions firmly establish the Hiyama reaction as a viable (even superior) alternative to the traditional Suzuki and Stille couplings In the retinoid field.