<i>O-</i>Acetyl 1,3-Propanediol as an Acrolein Proelectrophile in Enantioselective Iridium-Catalyzed Carbonyl Allylation

Verboom, Katherine L.; Meyer, Cole C.; Evarts, Madeline M.; Jung, Woo‐Ok; Krische, Michael J.

doi:10.1021/acs.orglett.3c01022

Cited by 1 publication

(1 citation statement)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…catalyze an exceptionally diverse array of highly enantioselective carbonyl allylations from alcohol proelectrophiles (Figure ). , The π-allyliridium− C , O -benzoate complex, which is stable to conventional silica gel chromatography, can exist as four possible diastereomeric-at-metal complexes. The relative energies of these complexes have been estimated by DFT calculations .…”

Section: Cyclometalated π-Allyliridium−co-benzoatesmentioning

confidence: 99%

Leveraging the Stereochemical Complexity of Octahedral Diastereomeric-at-Metal Catalysts to Unlock Regio-, Diastereo-, and Enantioselectivity in Alcohol-Mediated C–C Couplings via Hydrogen Transfer

Shezaf,

Santana,

Ortiz

et al. 2024

J. Am. Chem. Soc.

Self Cite

View full text Add to dashboard Cite

Experimental and computational studies illuminating the factors that guide metal-centered stereogenicity and, therefrom, selectivity in transfer hydrogenative carbonyl additions of alcohol proelectrophiles catalyzed by chiral-at-metal-and-ligand octahedral d 6 metal ions, iridium(III) and ruthenium(II), are described. To augment or invert regio-, diastereo-, and enantioselectivity, predominantly one from among as many as 15 diastereomeric-at-metal complexes is required. For iridium(III) catalysts, cyclometalation assists in defining the metal stereocenter, and for ruthenium(II) catalysts, iodide counterions play a key role. Whereas classical strategies to promote selectivity in metal catalysis aim for high-symmetry transition states, well-defined lowsymmetry transition states can unlock selectivities that are otherwise difficult to achieve or inaccessible.

show abstract

Section: Cyclometalated π-Allyliridium−co-benzoatesmentioning

confidence: 99%