We have developed a Pd catalyst featuring an electron deficient phosphinooxazoline (PHOX) ligand that effectively controls both the site- and enantioselectivity of hydrofunctionalization reactions of 1,3-dienes. In the presence of 5 mol% Pd catalyst at or below room temperature, acyclic 1,3-dienes undergo hydroamination and hydroalkylation in up to &gt;98% yield, &gt;20:1 site-selectivity, and 97.5:2.5 er. Unlike many other catalytic hydroamination reactions that only tolerate electron poor amine nucleophiles, this robust catalyst is compatible with electron rich aliphatic amines such as piperidine and pyrrolidine. Furthermore, the catalyst is tolerant of reactive functional groups such as alcohols and halides. Preliminary mechanistic investigations have revealed key insights into understanding the role of this catalytic system.

Homogenous Pd catalysis for enantioselective intermolecular hydrofunctionalizations of 1,3-dienes

255th National Meeting (2018)

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