Rh-catalyzed alkoxycarbonylation of unactivated alkyl chlorides

Abstract

An efficient and convenient rhodium-catalyzed alkoxycarbonylation of unactivated alkyl chlorides was developed for the first time. More than 80 examples of esters were prepared directly from readily available substrates with often high selectivity.

Photoinduced copper-catalyzed alkoxycarbonylation of alkyl fluorides

“…Based on the above results and literature reports, 7–14 we proposed a mechanism for this reaction (Scheme 4). Initially, the LCu I OAr species ( I ) was generated from the copper salt through ligand exchange with phenol and the ligand.…”

Rhodium‐Catalyzed Formylation of Unactivated Alkyl Chlorides to Aldehydes

“…This ligand was selected due to its superior performance in our recent work on the alkoxycarbonylation of alkyl chlorides. [10] Notably, using Rh(acac)(CO) 2 best activity as well as selectivity was observed. Next, different phosphine ligands were tested in the presence of this metal precursor.…”

“…Initially, we investigated the catalytic activity of different metal complexes of palladium, ruthenium, iridium, and rhodium in the presence of 1,3‐bisdiphenylphosphinopropane (DPPP) (Supporting Information, Table S1). This ligand was selected due to its superior performance in our recent work on the alkoxycarbonylation of alkyl chlorides [10] . Notably, using Rh(acac)(CO) 2 best activity as well as selectivity was observed.…”

Manganese-Catalyzed Alkoxycarbonylation of Alkyl Chlorides

“…However, the vast majority of the reported systems were limited to C­(sp 3 )–iodides, bromides, and sulfonates (Scheme A). The development of a method applicable to simple alkyl chlorides has been a long-standing goal of the field. − …”