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Carboxylate-directed Mizoroki-Heck.pdf (732.52 kB)
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Intermolecular Heck Coupling with Hindered Alkenes Driven by Carboxylate Directivity

preprint
submitted on 13.10.2018 and posted on 15.10.2018 by Tucker R. Huffman, Yebin Wu, Alexis Emmerich, Ryan Shenvi

Pd(0)-catalyzed, non-chain-walking Mizoroki-Heck reactions exhibit poor reactivity with polysubsti- tuted, unbiased alkenes. Intermolecular reactions with simple, all-carbon tetrasubstituted alkenes are unprecedented. Here we report that pendant carboxylic acids, combined with bulky monophospine ligands on palladium, can direct the arylation of tri- and tetrasubstituted olefins. Quaternary carbons are established at high Fsp3 attached-ring junctures and the carboxylate directing group can be removed after coupling. Carboxylate directivity prevents over-arylation of the new, less hindered alkene, which can be diversified in subsequent reactions.

Funding

R35 GM122606

History

Email Address of Submitting Author

rshenvi@scripps.edu

Institution

The Scripps Research Institute

Country

USA

ORCID For Submitting Author

0000-0001-8353-6449

Declaration of Conflict of Interest

No conflict of interest

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