By Bethany Halford
Reprinted from C&EN
Although chemists have plenty of ways to add carbon atoms to alkenes—including the
Nobel Prize-winning Heck reaction—they have fewer options when working with heteroatom
nucleophiles, such as alcohols. Now, Matthew S. Sigman and his group at the University of Utah report an intermolecular oxa-Heck reaction that allows
them to couple phenols with allylic alcohols in an enantioselective manner (J. Am. Chem. Soc. 2016, DOI: 10.1021/jacs.6b11486). The reaction, which is catalyzed by palladium in the presence of a chiral pyridine
oxazoline ligand, creates building blocks that would be tough to make using more common
synthetic reactions, such as a Michael addition (example shown). Sigman’s team selected
allylic alcohols as the alkene in the reaction in order to influence which hydrogen
would be removed during the β-elimination to form the chiral product. The chemists
show the reaction works with a broad scope of allylic alcohols and phenols, and even
successfully swaps the phenol for cumene hydroperoxide in several examples. Next,
they plan to explore the scope of the reaction with other heteroatom nucleophiles
that are compatible with the coupling strategy.
- Chemical & Engineering News
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- Copyright © 2016 American Chemical Society