Ruthenium pincer complex-catalyzed heterocycle compatible alkoxycarbonylation of alkyl iodides: substrate keeps the catalyst active

Abstract

The electron pair of the heteroatom in heterocycles will coordinates with metal catalysts and decreasing or even inhibit their catalytic activity consequently. In this work, a pincer ruthenium-catalyzed heterocyclic compatible...

Manganese-Catalyzed Alkoxycarbonylation of Alkyl Chlorides

“…Based on the above results and previous reports, − we proposed a plausible mechanism for this alkoxycarbonylation event (Scheme ). Initially, active manganese complex Int-I will be formed under the assistance of the base.…”

“…Our study began by evaluating the alkoxycarbonylation of 1-chlorobutane 1 and alcohol 2 . When metal precursors such as cobalt, iron, and ruthenium were used, no desired carbonylative coupling product 3 could be detected (Table , entries 1–2). Fortunately, as shown in entry 3, the PNP-type pincer/Mn complex Mn-1 exerted promising results.…”

“…In recent years, pincer complexes have gained considerable attention as efficient inert chemical bond-activation catalysts and are promising to offer new chances in synthetic technology. − Among them, Neumann and Skrydstrup and we recently sought to employ pincer complexes as mediators or catalyst for the development of radical-mediated carbonylation in an effort to significantly reduce the deactivating coordination effect caused by overcoordinating of CO and heterocycles to the metal center. However, since the C­(sp 3 )–Cl bond is more inert than the C­(sp 3 )–Br and C­(sp 3 )–I bonds, the homolysis of the C­(sp 3 )–Cl bond is intractable under the pincer metal-assisted SET strategy.…”

Abundant metal-catalyzed carbonylation of alkyl bromides and alkyl chlorides

“…However, the carbonylation of C(sp 3 )–X bonds, particularly those of unactivated alkyl halides, is relatively challenging compared to that of aryl halides due to the difficulty of oxidative addition and competing β-elimination reactions. 5 Based on the continuous efforts of organic chemists, particularly the pioneering studies of Heck, Alper, Ryu and others, 6 and the intensive research of Arndtsen, 7 Mankad 8 and our group 9 in recent years, many carbonylation proposals for alkyl halides based on transition metal-catalyzed or photoinduced single-electron transfer (SET) processes have been successfully established. However, most of the research studies on the carbonylation of alkyl halides have focused on more active alkyl iodides, while the carbonylation reactions of less active and inexpensive alkyl bromides and alkyl chlorides have been rarely reported.…”

Copper-Catalyzed Direct Carbonylation of Carbenes toward the Synthesis of Propanedioic Acid Derivatives

“…N , N -Diphenylamine has been proven to be a suitable substate, as well, and a 63% yield of the corresponding product was isolated ( 4ag ). Heterocycles are often incompatible with metal catalysts, as the heteroatom may coordinate with the metal catalyst . In the reaction, the amines with heterocyclic rings were not affected and the target products were obtained in good yields ( 4ah–4aj ).…”