PdI2-Based Catalysis for Carbonylation Reactions: A Personal Account

Abstract

In this account, we review our efforts in the field of carbonylation reactions promoted by palladium iodide-based catalysts, which have proven to be particularly efficient in diverse kinds of carbonylation processes (oxidative carbonylations as well as additive and substitutive carbonylations). Particularly in the case of oxidative carbonylations, more emphasis has been given to the most recent results and applications.

A Stereoselective, Multicomponent Catalytic Carbonylative Approach to a New Class of α,β-Unsaturated γ-Lactam Derivatives

“…Based on the existing knowledge on carbonylations [1][2][3][4][5] and on our expertise in PdI 2 /KI-catalyzed carbonylation reactions [7,8], we can propose the mechanistic pathway shown in Scheme 2 for the formation of (Z)-2-(2-oxopyrrolidin-3-ylidene)acetates 2. Palladation of the nitrogen of 1 initially leads to alkynylaminopalladium intermediate I, stabilized by the intramolecular triple bond coordination (anionic iodide ligands are omitted for clarity).…”

“…In this work, a stereoselective, multicomponent catalytic carbonylative approach to a new class of α,β-unsaturated γ-lactam derivatives, that are, alkyl (Z)-2-(2-oxopyrrolidin-3ylidene)acetates 2, is presented. The synthetic approach is based on the use of a particularly simple catalytic system, consisting of PdI 2 in conjunction with KI [7,8], for the catalytic activation of very simple starting materials (homopropargylic amines 1, carbon monoxide, an alcohol, and oxygen; Scheme 1).…”

Synthesis of Luminescent Fused Imidazole Bicyclic Acetic Esters by a Multicomponent Palladium Iodide‐Catalyzed Oxidative Alkoxycarbonylation Approach

“…Of particular interest are those methods that are based on sequential heterocyclization‐alkoxycarbonylation of suitably functionalized alkynes, which may lead to heterocyclic esters in one step starting from readily available starting materials [2] . In this field, our research group has contributed many examples, [3] by employing a very simple catalytic system based on PdI 2 in conjunction with KI, as reviewed in our recently published account [1f] …”

Pd-Catalyzed Cyclocarbonylation of Allylic Alcohol under Benign Conditions with Ionic Liquid as Stabilizer

“…Several reviews are available in the literature on reactions and mechanisms of transition-metal catalyzed carbonylation and cyclocarbonylation for lactone production using Group [10][11][12][13][14][15][16]. With noble-metal catalysts, Pd has played an almost exclusive role in lactonization almost exclusive role in lactonization reactions as it generally provides higher yields of lactones compared to other catalysts [13,14].…”

“…Several reviews are available in the literature on reactions and mechanisms of transition-metal catalyzed carbonylation and cyclocarbonylation for lactone production using Group [10][11][12][13][14][15][16]. With noble-metal catalysts, Pd has played an almost exclusive role in lactonization almost exclusive role in lactonization reactions as it generally provides higher yields of lactones compared to other catalysts [13,14]. In particular, an interesting cyclocarbonylation catalyst system based on Pd-dppb (dppb: 1,4-bis-(diphenylphosphino)butane) was introduced by Ali and Alper [1] and Brunner and Alper [17] for the formation of γ-lactones from secondary-, tertiary-as well as β,γsubstituted allylic alcohols under neutral but quite harsh reaction conditions (40-54 bar CO/H2, 110-190 °C, 18-48 h).…”