Palladium-Catalyzed Vinylation of Cyclopentenes with Inverted Z,E-Isomerism of Vinylic Substrates

A palladium-promoted Mizoroki-Heck type reaction employing a directing-group strategy to efficiently produce the coupled vinyl cyclopentenes with excellent regio- and stereoselectivity is reported. Typically, a Pd-catalyzed reaction of 2-(cyclopent-2-en-1-yl)-N-tosylacetamide (1a) with (E)-styryl bromides gave cis-2-((Z)-styryl)cyclopent-3-en-1-yl-N-tosylacetamide (3e), an allylic substitution product. Interestingly, we have found that the E,Z-stereochemistry of vinylic substrates is inverted in those products. The mechanism of this catalytic reaction is discussed.

Automated summary

A palladium-promoted Mizoroki-Heck type reaction using a directing-group strategy efficiently produces coupled vinyl cyclopentenes with excellent regio- and stereoselectivity. Interestingly, it was found that the stereochemistry of the vinylic substrates is inverted in the products.