Unknown

Dataset Information

0

Sustainable Pd(OAc)2 /Hydroquinone Cocatalyst System for Cis-Selective Dibenzoyloxylation of 1,3-Cyclohexadiene.

ABSTRACT: The 1,4-diacyloxylation of 1,3-cyclohexadiene (CHD) affords valuable stereochemically defined scaffolds for natural product and pharmaceutical synthesis. Existing cis-selective diacyloxylation protocols require superstoichiometric quantities of benzoquinone (BQ) or MnO2 , which limit process sustainability and large-scale application. In this report, reaction development and mechanistic studies are described that overcome these limitations by pairing catalytic BQ with tert-butyl hydroperoxide as the stoichiometric oxidant. Catalytic quantities of bromide enable a switch from trans to cis diastereoselectivity. A catalyst with a 1:2 Pd:Br ratio supports high cis selectivity while retaining good rate and product yield. Further studies enable replacement of BQ with hydroquinone (HQ) as a source of cocatalyst, avoiding the handling of volatile and toxic BQ in large-scale applications.

SUBMITTER: Stamoulis AG 

PROVIDER: S-EPMC8511170 | biostudies-literature | 2021 Oct

REPOSITORIES: biostudies-literature

Json Xml
altmetric image

Publications

Sustainable Pd(OAc)<sub>2</sub> /Hydroquinone Cocatalyst System for Cis-Selective Dibenzoyloxylation of 1,3-Cyclohexadiene.

Stamoulis Alexios G AG   Geng Peng P   Schmidt Michael A MA   Eastgate Martin D MD   Borovika Alina A   Fraunhoffer Kenneth J KJ   Stahl Shannon S SS  

Angewandte Chemie (International ed. in English) 20210917 43

The 1,4-diacyloxylation of 1,3-cyclohexadiene (CHD) affords valuable stereochemically defined scaffolds for natural product and pharmaceutical synthesis. Existing cis-selective diacyloxylation protocols require superstoichiometric quantities of benzoquinone (BQ) or MnO<sub>2</sub> , which limit process sustainability and large-scale application. In this report, reaction development and mechanistic studies are described that overcome these limitations by pairing catalytic BQ with tert-butyl hydro  ...[more]

Similar Datasets

Unknown Benzoquinone Cocatalyst Contributions to DAF/Pd(OAc)<sub>2</sub>-Catalyzed Aerobic Allylic Acetoxylation in the Absence and Presence of a Co(salophen) Cocatalyst.
| S-EPMC8373043 | biostudies-literature
Unknown Can Donor Ligands Make Pd(OAc)<sub>2</sub> a Stronger Oxidant? Access to Elusive Palladium(II) Reduction Potentials and Effects of Ancillary Ligands via Palladium(II)/Hydroquinone Redox Equilibria.
| S-EPMC7678807 | biostudies-literature
Unknown Pd(OAc)<sub>2</sub>-catalyzed asymmetric hydrogenation of sterically hindered N-tosylimines.
| S-EPMC6258694 | biostudies-literature
Unknown Cu/Pd-catalyzed arylboration of a 1-silyl-1,3-cyclohexadiene for stereocontrolled and diverse cyclohexane/ene synthesis.
| S-EPMC10548526 | biostudies-literature
Unknown Reactivity of a Dinuclear Pd<sup>I</sup> Complex [Pd<sub>2</sub>(μ-PPh<sub>2</sub>)(μ<sub>2</sub>-OAc)(PPh<sub>3</sub>)<sub>2</sub>] with PPh<sub>3</sub>: Implications for Cross-Coupling Catalysis Using the Ubiquitous Pd(OAc)<sub>2</sub>/nPPh<sub>3</sub> Catalyst System.
| S-EPMC8441971 | biostudies-literature
Unknown Pd(OAc)<sub>2</sub>/Ph<sub>3</sub>P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles.
| S-EPMC5588454 | biostudies-literature
Unknown Synthesis of eunicellane-type bicycles embedding a 1,3-cyclohexadiene moiety.
| S-EPMC6176824 | biostudies-literature
Unknown Pd-Senphos Catalyzed trans-Selective Cyanoboration of 1,3-Enynes.
| S-EPMC7491284 | biostudies-literature
Unknown On the Unique Reactivity of Pd(OAc)<sub>2</sub> with Organic Azides: Expedient Synthesis of Nitriles and Imines.
| S-EPMC3752930 | biostudies-literature
Unknown Photochemical Ring-Opening Reaction of 1,3-Cyclohexadiene: Identifying the True Reactive State.
| S-EPMC9732879 | biostudies-literature