Manganese-Catalyzed Alkoxycarbonylation of Alkyl Chlorides

Abstract

The carbonylative transformation of alkyl chlorides, a class of cheap chemical feedstock, is among the most challenging tasks in the field of carbonylation due to the difficulty of C(sp3)–Cl bond activation. Herein, we report the catalytic alkoxycarbonylation of unactivated alkyl chlorides. This method employs a pincer manganese catalyst to overcome the intrinsic limitations of C(sp3)–Cl bond activation and allows access to various esters in a straightforward manner. Mechanistic studies indicate that the alkyl chlorides were activated directly via an oxidative addition reaction.

Recent Advances in Base‐Metal‐Catalyzed Carbonylation of Unactivated Alkyl Electrophiles†

“…In 2022, Wu and co‐workers successfully developed a manganese‐catalyzed alkoxycarbonylation of unactivated alkyl chlorides (Scheme 18). [ 40 ] This method employed a pincer manganese catalyst to overcome the intrinsic limitations of C(sp 3 )−Cl bond activation and allowed access to various esters in moderate to good yields. Primary alkyl chlorides with various functional groups, such as ethers, acetyl, Bpin were all applicable, while secondary and benzyl alkyl chlorides gave the products in lower yields.…”

Abundant metal-catalyzed carbonylation of alkyl bromides and alkyl chlorides

“…18 To overcome the difficulties, we used pincer complexes as efficient inert chemical bond activation catalysts and “harder” manganese metal to improve the oxidative addition capacity of manganese metal, thus successfully achieving the alkoxycarbonylation of abundant, cheap, and less toxic alkyl chlorides (Scheme 5a). 19 This pincer manganese catalyzed alkoxycarbonylation system of alkyl chlorides is applicable to primary alcohols, secondary alcohols, and benzyl alcohols, all showing excellent performance in obtaining esters in good to excellent yields. Unfortunately, tertiary alcohols were used as substrates in low yields, and phenol and allyl alcohol could not even participate in the reaction.…”

Recent Advances in Nonprecious Metal Catalysis

“…The Wu group also reported a similar procedure, this time catalyzed by a pincer manganese complex, that enables the use of alkyl chlorides as substrates (Scheme 8). 28 Wu and co-workers proposed that the Mn complex activates alkyl chlorides by oxidative addition, as opposed to a SET pathway. The reported conditions are compatible with primary, secondary, and benzylic alcohols and primary, secondary, and benzylic alkyl chlorides.…”