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Tandem Blaise/retro-Blaise Reaction for the Nitrile-Mediated Regioselective Intermolecular Addition of Unstabilized Zinc Ester Enolates (Reformatsky Reagents) to 1‑Alkynes and 1,3-Enynes

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posted on 2013-11-15, 00:00 authored by Ju Hyun Kim, Yu Sung Chun, Sang-gi Lee
We report the novel use of a nitrile as a mediator to achieve the regioselective intermolecular addition of unstabilized zinc ester enolates (Reformatsky reagents) to 1-alkynes and 1,3-enynes. This reaction is made possible by a reversible addition of enolates to a nitrile (Blaise reaction), generating a zinc aza-enolate that, unlike zinc ester enolates, can add intermolecularly to 1-alkynes and 1,3-enynes. Subsequent removal of the nitrile through a retro-Blaise reaction generates the targeted addition product. This method is combined with a Diels–Alder reaction and subsequent oxidative aromatization, providing a tandem one-pot de novo construction of α-arylated alkanoates from Reformatsky reagents.

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