Understanding catalyst structure-selectivity relationships in Pd-catalyzed enantioselective methoxycarbonylation of styrene

Simone Gallarati, Paul Dingwall, José Antonio Fuentes García, Michael Buehl, Matthew L. Clarke

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18 Citations (Scopus)
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Abstract

Catalyst-controlled regioselectivity in palladium-catalyzed carbonylation of alkenes has been a long-standing goal of homogeneous catalysis. In general, monophosphines do favor branched regioselectivity, but lead to poor enantioselectivity, while diphosphines give mainly linear products. Previously, we reported the simultaneous control of regio- and enantioselectivity in the hydroxy- and methoxycarbonylation of vinyl arenes with Pd complexes of the Phanephos ligand. Herein, we present a density functional theory study (B3PW91-D3 level of theory) of the catalytic cycle, supported by deuterium labeling studies, to understand its mechanism. Alkene coordination to a Pd-hydride species was identified as the origin of asymmetric induction and regioselectivity in both the parent Pd/Xylyl-Phanephos catalyst and electron-deficient analogue, and rationalized according to a quadrant-diagram representation. The mechanism by which the preferentially formed pro-(S) Pd-alkene complex can isomerize via rotation around the palladium–(C═C) bond was investigated. In the parent system, this process is in competition with the methanolysis step that leads to the ester product and is responsible for the overall loss of regioselectivity. On the other hand, the introduction of electron-withdrawing substituents on the catalyst framework results in the reduction of the methanolysis barriers, making the isomerization pathway energetically unfavorable and so leading simultaneously to high regiocontrol and good enantiomeric ratios.
Original languageEnglish
Number of pages13
JournalOrganometallics
VolumeArticles ASAP
Early online date14 Dec 2020
DOIs
Publication statusE-pub ahead of print - 14 Dec 2020

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