Reactivity of Stabilized Vinyldiazo Compounds toward Alkenyl- and Alkynylsilanes under Gold Catalysis: Regio- and Stereoselective Synthesis of Skipped Dienes and Enynes

We report the gold-catalyzed reaction of vinyldiazo compounds and alkenylsilanes to produce skipped dienes, which are common structural motifs in an array of bioactive compounds. This carbon-carbon bond-forming transformation proceeds with complete regio- and stereoselectivity with the silyl group serving as a regio- and stereocontrolling element. Likewise, the use of alkynylsilanes as reaction partners yielded skipped enynes resulting from a C(sp)-C(sp(3)) coupling. Mechanistic experiments and DFT studies have provided support for a stepwise mechanism.

Automated summary

This study reports the gold-catalyzed reaction of vinyldiazo compounds and alkenylsilanes to produce skipped dienes, common structural motifs in bioactive compounds. The reaction proceeds with complete regio- and stereoselectivity, with the silyl group serving as a regio- and stereocontrolling element. Additionally, the use of alkynylsilanes as reaction partners yielded skipped enynes through C(sp)-C(sp(3)) coupling.