English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Zendy Plus

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Zendy Tools

Zendy Open

The detailed mechanism of the hydroacylation of β-amido-aldehyde, 2,2-dimethyl-3-morpholino-3-oxopropanal, with 1-octyne using [Rh( cis-κ 2 - P,P -DPEPhos)(acetone) 2 ][BAr F  4 ]-based catalysts, is described [Ar F = (CF 3 ) 2 C 6 H 3 ]. A rich mechanistic landscape of competing and interconnected hydroacylation and cyclotrimerization processes is revealed. An acyl-hydride complex, arising from oxidative addition of aldehyde, is the persistent resting state during hydroacylation, and quaternary substitution at the β-amido-aldehyde strongly disfavors decarbonylation. Initial rate, KIE, and labeling studies suggest that the migratory insertion is turnover-limiting as well as selectivity determining for linear/branched products. When the concentration of free aldehyde approaches zero at the later stages of catalysis alkyne cyclotrimerization becomes competitive, to form trisubstituted hexylarenes. At this point, the remaining acyl-hydride turns over in hydroacylation and the free alkyne is now effectively in excess, and the resting state moves to a metallacyclopentadiene and eventually to a dormant α-pyran-bound catalyst complex. Cyclotrimerization thus only becomes competitive when there is no aldehyde present in solution, and as aldehyde binds so strongly to form acyl-hydride when this happens will directly correlate to catalyst loading: with low loadings allowing for free aldehyde to be present for longer, and thus higher selectivites to be obtained. Reducing the catalyst loading from 20 mol % to 0.5 mol % thus leads to a selectivity increase from 96% to ∼100%. An optimized hydroacylation reaction is described that delivers gram scale of product, at essentially quantitative levels, using no excess of either reagent, at very low catalyst loadings, using minimal solvent, with virtually no workup.

journal of the american chemical society

Rh(DPEPhos)-Catalyzed Alkyne Hydroacylation Using β-Carbonyl-Substituted Aldehydes: Mechanistic Insight Leads to Low Catalyst Loadings that Enables Selective Catalysis on Gram-Scale