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Palladium-catalyzed ?,?-dehydrogenation of acyclic ester equivalents promoted by a novel electron deficient phosphinooxazoline ligand.


ABSTRACT: A unique example of Pd-catalyzed decarboxylative dehydrogenation of fully substituted N-acyl allyl enol carbonates is enabled by a new electron deficient phosphinooxazoline (PHOX) ligand. The reaction proceeds from the Z-enol carbonate to provide dehydrogenation products exclusively in high E/Z selectivity, while the E-enol carbonate provides the ?-allylation product with only minor dehydrogenation. The reaction proceeds with a broad scope of (Z)-enol carbonates derived from N-acyl indoles to furnish acyclic formal ?,?-unsaturated ester equivalents.

SUBMITTER: Fulton TJ 

PROVIDER: S-EPMC7119178 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature

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Palladium-catalyzed α,β-dehydrogenation of acyclic ester equivalents promoted by a novel electron deficient phosphinooxazoline ligand.

Fulton Tyler J TJ   Wu Brenda B   Alexy Eric J EJ   Zhang Haiming H   Stoltz Brian M BM  

Tetrahedron 20190601 31


A unique example of Pd-catalyzed decarboxylative dehydrogenation of fully substituted <i>N</i>-acyl allyl enol carbonates is enabled by a new electron deficient phosphinooxazoline (PHOX) ligand. The reaction proceeds from the <i>Z</i>-enol carbonate to provide dehydrogenation products exclusively in high <i>E/Z</i> selectivity, while the <i>E</i>-enol carbonate provides the α-allylation product with only minor dehydrogenation. The reaction proceeds with a broad scope of (<i>Z</i>)-enol carbonate  ...[more]

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