New Directions in Transition Metal Catalyzed Carbonylation Chemistry

Abstract

Carbon monoxide (CO) represents an important C1-building block for the construction of some of the most fundamental chemical functionalities carrying a carbon–oxygen double bond. Transition metal catalysis plays a key role in promoting such transformations. We have earlier shown that the combination of palladium catalysis with CO releasing molecules and the two-chamber reactor, COware, provides a convenient and safe means for performing traditional Pd-catalyzed carbonylative couplings, as well as being a platform for the discovery of new carbonylation reactions. Furthermore, the method can be adapted to 13C- and 14C-isotope labeling, as well as providing for a suitable setting for developing efficient carbonylation reactions with 11CO. Herein, we provide a short overview of our latest findings in this area with emphasis on carbonylative couplings with fluorinated building blocks, but also discuss our efforts to develop viable Ni-catalyzed carbonylations with aliphatic substrates, which can be performed efficiently under low CO partial pressures.

Palladium‐Catalyzed Tunable Carbonylative Synthesis of Enones and Benzofulvenes

“…Among the various transition‐metal‐catalyzed transformations, the carbonylative reaction is an efficient method for incorporating C1 synthons into organic compounds to give various carbonyl‐containing compounds . From the point view of diversity, the transition‐metal‐catalyzed arylcarbonylative coupling of internal alkynes with aryl halides and organometallic compounds should provide an efficient and direct method for the synthesis of tetrasubstituted enones and related compounds.…”

“…[9][10][11][12][13] From the point view of diversity,t he transition-metal-catalyzed arylcarbonylative coupling of internal alkynes with aryl halidesa nd organometallic compounds should provide an efficient and direct method for the synthesis of tetrasubstituted enones and relatedc ompounds. [9][10][11][12][13] From the point view of diversity,t he transition-metal-catalyzed arylcarbonylative coupling of internal alkynes with aryl halidesa nd organometallic compounds should provide an efficient and direct method for the synthesis of tetrasubstituted enones and relatedc ompounds.…”

COtab: Expedient and Safe Setup for Pd-Catalyzed Carbonylation Chemistry

“…In 2011, we reported on the ex situ formation of CO from a crystalline acid chloride (COgen), which enabled the safe liberation of this diatomic molecule in a two-chamber system (COware) . Since then, we have reported on numerous carbonylative transformations utilizing this setup . Although the safety concern can be eliminated by applying this strategy in small-scale reactions, it is still not without its drawbacks as the methodology requires an inert atmosphere, and therefore, reactions are set up in a glovebox.…”

Mechanistic Insights into the Palladium-Catalyzed Perfluoroalkylative Carbonylation of Unactivated Alkenes to β-Perfluoroalkyl Esters: A DFT Study

“…Therefore, an efficient synthesis method for multifunctional esters is required. Conventional esterification is usually generated by the reactions of carboxylic acids and alcohols under acid or base conditions, resulting in low yields and requiring multistep synthesis. − Meanwhile, a series of multifunctional esters have been synthesized by transition metal-catalyzed carbonylation reactions, − displaying more atomically economical properties, fewer synthetic steps, and higher yields than conventional esterification. , Therefore, transition metal-catalyzed carbonylation reactions have been regarded as one of the most promising approaches for the functionalization of carboxylic acid esters.…”

“…12−14 Meanwhile, a series of multifunctional esters have been synthesized by transition metal-catalyzed carbonylation reactions, 15−20 displaying more atomically economical properties, fewer synthetic steps, and higher yields than conventional esterification. 21,22 Therefore, transition metalcatalyzed carbonylation reactions have been regarded as one of the most promising approaches for the functionalization of carboxylic acid esters.…”