Suzuki cross-coupling of haloalkenes is generally assumed to occur with retention of the alkene stereochemistry. While studying Suzuki cross-couplings on E-1,2-dichlorovinyl phenyl ketone, we were surprised to observe extensive isomerization. More surprisingly, the ligand employed strongly influenced the degree of isomerization: DPEphos and Xantphos led to 96% isomerized cross-coupled product whereas reactions in the absence of a phosphine ligand, or reactions employing t-BuXantphos, gave 94% retention of stereochemistry. While E–Z isomerization in Pd-catalyzed vinylic couplings has previously been attributed to events within the cross-coupling catalytic cycle, we present experimental and computational evidence for a separate Pd-catalyzed isomerization process in these reactions.
E - Z isomerization in Suzuki cross-couplings of haloenones: Ligand effects and evidence for a separate catalytic cycle / Chehal, N. K.; Budzelaar, P. H. M.; Hultin, P. G.. - In: ORGANIC & BIOMOLECULAR CHEMISTRY. - ISSN 1477-0520. - 16:7(2018), pp. 1134-1143. [10.1039/c7ob02925j]
E - Z isomerization in Suzuki cross-couplings of haloenones: Ligand effects and evidence for a separate catalytic cycle
Budzelaar, P. H. M.;
2018
Abstract
Suzuki cross-coupling of haloalkenes is generally assumed to occur with retention of the alkene stereochemistry. While studying Suzuki cross-couplings on E-1,2-dichlorovinyl phenyl ketone, we were surprised to observe extensive isomerization. More surprisingly, the ligand employed strongly influenced the degree of isomerization: DPEphos and Xantphos led to 96% isomerized cross-coupled product whereas reactions in the absence of a phosphine ligand, or reactions employing t-BuXantphos, gave 94% retention of stereochemistry. While E–Z isomerization in Pd-catalyzed vinylic couplings has previously been attributed to events within the cross-coupling catalytic cycle, we present experimental and computational evidence for a separate Pd-catalyzed isomerization process in these reactions.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.