Cooperative catalytic methoxycarbonylation of alkenes: uncovering the role of palladium complexes with hemilabile ligands

Abstract

Mechanistic studies of the catalyst [Pd2(dba)3/1,1′-bis(tert-butyl(pyridin-2-yl)phosphanyl)ferrocene, L2] for olefin alkoxycarbonylation reactions are described.

Synthesis of Carboxylic Acids by Palladium‐Catalyzed Hydroxycarbonylation

“…[53,54] Recently,w ed eveloped bidentate ligands with integral basic sites (pyridyl-substituted phosphines), which act as aproton shuttle and improve the rate-determining esterification step in alkoxycarbonylation reactions. [55][56][57] Furthermore, we demonstrated the superiority of these ligands for selective formic acid decomposition reactions. [58] Based on that work, we became interested in studying the stability of the related catalysts in hydroxycarbonylation reactions.A saresult, herein we present the most stable and general hydroxycarbonylation catalyst known to date.…”

“…In this respect, the groups of Monflier and later on Ionescu investigated the recyclability of watersoluble Pd-catalysts. [55][56][57] Furthermore, we demonstrated the superiority of these ligands for selective formic acid decomposition reactions. [51,52] However,i nt his patent the stability of the recycled catalyst is not reported and it is only stated that the catalyst system was "almost exclusively detected in the organic phase".…”

Controlling the Depolymerization of Paraformaldehyde with Pd–Phosphine Complexes

“…The mechanism of carbonylation reactions is well understood when CO gas is used. [18] In contrast to this there are very few reports that investigate the reaction mechanism when aC Os urrogate is used insteado fC Og as [19][20][21] and unfortunately even less is knowna bout the depolymerization of paraformaldehyde [22,23] in solution and the influence of homogeneous catalysts on the depolymerization process.…”

Pd‐Catalyzed Selective Carbonylation of gem‐Difluoroalkenes: A Practical Synthesis of Difluoromethylated Esters

“…[27] Recently,w ed emonstrated the advantage of specific phosphine ligands with built-in base function for Pd-catalyzed alkoxycarbonylations of less-reactive olefins including hindered tetra-substituted alkenes. [25] Hence,atthe start of our studies,weinvestigated the influence of these and related standard ligands for the methoxycarbonylation of 2-(2,2-difluorovinyl)naphthalene 1a under typical carbonylation conditions for alkenes (Table 1). [25] Hence,atthe start of our studies,weinvestigated the influence of these and related standard ligands for the methoxycarbonylation of 2-(2,2-difluorovinyl)naphthalene 1a under typical carbonylation conditions for alkenes (Table 1).…”