Pd-Catalyzed Regioselective Alkoxycarbonylation of 1-Alkenes Using a Lewis Acid [SnCl₂ or Ti(OⁱPr)₄] and a Phosphine

Abstract

The phosphine ligand mediated palladium catalyzed alkoxycarbonylation of alkenes was investigated with the objective of attaining good linear selectivity for the ester. The effect of various parameters such as solvents, additives, palladium precursors, CO pressures, and alkenes of various structural complexities were examined. The results revealed the importance of using a Lewis acid such as SnCl2 or Ti(O(i)Pr)4 in combination with a monodentate ligand such CYTOP 292 or P(p-anisyl)3 to enhance the regioselectivity for the linear isomers in the range of 70-96%.

Kinetic Modeling of the Palladium‐Catalyzed Isomerizing Methoxycarbonylation of 1‐Decene

“…In all experiments, the highest yield of 79 % n ‐methyl ester was determined for 5 bar CO at 95 °C after 180 min. Comparable catalytic results for terminal long chain olefins were already reported , . The Pd/DTBPMB‐catalyzed methoxycarbonylation is characterized by a fast isomerization of 1‐decene to iso ‐decenes with respect to the n ‐selective methoxycarbonylation (Fig.…”

“…Unsaturated oleochemicals from renewables like glycerides, methyl oleate and methyl 10‐undecenoate (UME) have also been proven to be attractive substitutes for petrochemical substrates in the palladium‐catalyzed methoxycarbonylation producing α , ω ‐functionalized intermediates for the production of polyesters and polyamides . For a sustainable and economic catalytic process, the reuse of the catalyst plays a key role.…”

Kinetic models of the cyclohexene hydromethoxycarbonylation catalyzed by the Pd(OAc)2/trans‐2,3‐bis(diphenylphosphinomethyl)norbornane/p‐toluensulfonic acid

“…Homogeneous catalytic systems based on palladium compounds promoted by free phosphines show the highest activity in this reaction. In recent years, using these systems, hydrocarbalkoxylation of hexene‐1, cyclohexene, octene‐1, and alkenes C 8 –C 14 of various structural complexity, styrene hydromethoxycarbonylation which was regioselective by branched structure product and enantioselective styrenes hydrocarbalkoxylation by 4‐substituted phenols with aryl propanoates formation have been carried out. In the latter case, achiral mono‐/bidentate and chiral (enantiopure) bidentate phosphine ligands have been used as promoters.…”

From Carboxytelomerization of 1,3‐Butadiene to Linear α,ω‐C10‐Diester Combinatoric Approaches for an Efficient Synthetic Route

“…[5][6][7][8][9] In recent years, the methoxycarbonylation and the carbonylation of allylic compounds have become reactions with high industrial and academic impact. [10][11][12][13] Very recently, the designo fan ew ligand, the 1,2-bis((tert-butyl)pyridine-2yl)phosphanyl)methyl)benzene (py t bpx) set an ew benchmark of ethenec arbonylation competing with the application of the existing 1,2-bis(tert-butyl)phosphanyl)methyl)benzene (1,2-DTBPMB)l igand,w hich allows for extremelyh igh conversion rates in the palladium-catalysed methoxycarbonylation (TOF: 40,000 h À1 )w ith selectivity higher than 99 %o ft he generated esters. [14] The carboxytelomerization is an elegant carbonylationr eaction to directly obtain aC 9 -monoester as an intermediate of the targeted C 10 -diester 3 synthesis based on 1,3-butadiene 1.…”