Skip to main content
Open Access Publications from the University of California

UC Berkeley

UC Berkeley Previously Published Works bannerUC Berkeley

Reactivity and Selectivity Controlling Factors in the Pd/Dialkylbiarylphosphine-Catalyzed C-C Cleavage/Cross-Coupling of an N-Fused Bicyclo α-Hydroxy-β-Lactam.

Published Web Location
No data is associated with this publication.

Density functional theory was employed in order to elucidate the mechanism and factors that lead to the observed regioselectivity in the dialkylbiarylphosphine (Phos)/Pd-catalyzed C-C cleavage/cross-coupling of an N-fused bicyclo α-hydroxy-β-lactam, 1. We have identified that (a) a complex [(1)(Cs2CO3)]-PdL(PhBr) forms prior to a "base-mediated oxidative addition"; (b) Cs-carbonate (rather than a halide) deprotonates the alcohol substrate in the lowest energy pathway en route to Pd-alcoholate formation; (c) reactions using Phos ligands bearing OCF3 and OCF2H substituents on the "B"-ring are predicted to be selective toward proximal ring opening of 1; (d) steric repulsion between the bottom "B"-ring of the Phos ligand and the piperidine moiety of 1 controls the regioselectivity of the C-C cleavage followed by cross-coupling; and (e) the α- vs β-selective functionalization of the piperidine moiety in 1 is influenced by the bulkiness of the R2-substituent of the coupling partner. These studies will aid in the design of selective functionalizations of the piperidine moiety in 1.

Many UC-authored scholarly publications are freely available on this site because of the UC's open access policies. Let us know how this access is important for you.

Item not freely available? Link broken?
Report a problem accessing this item