Catalytic carbonylations of organohalides are important C–C bond formations in chemical synthesis. Carbonylations of unactivated alkyl halides remain a challenge, and currently require the use of alkyl iodides under harsh conditions and high pressures of CO. Herein, we report a palladium-catalyzed alkoxycarbonylation of secondary alkyl bromides that proceeds at low pressure (2 atm CO) under mild conditions. Preliminary mechanistic studies are consistent with a hybrid organometallic-radical process. These reactions efficiently deliver esters from unactivated alkyl bromides across a diverse range of substrates and represent the first catalytic carbonylations of alkyl bromides with carbon monoxide.

Despite advances in organometallic cross coupling of alkyl electrophiles, there are few stereoselective reactions of chiral, non-racemic substrates. Herein, we report a stereospecific carbonylative coupling of alkyl tosylates and dienes producing enantioenriched dienones. This catalytic process proceeds under low pressure and mild conditions using a simple cobalt catalyst and extends to diverse tosylate and diene coupling partners. The transformation constitutes a unique, convergent approach to the asymmetric synthesis of valuable carbonyl compounds from easily accessed starting materials.

Metal-catalyzed aminocarbonylation is as tandard approach for installing amide functionality in chemical synthesis.D espite broad application of this transformation using aryl or vinyl electrophiles,t here are few examples involving unactivated aliphatic substrates.F urthermore,t here are no stereocontrolled aminocarbonylations of alkyl electrophiles known. Herein, we report astereospecific aminocarbonylation of unactivated alkylt osylates for the synthesis of enantioenriched amides.T his cobalt-catalyzed transformation uses ar emarkably broad range of amines and proceeds with excellent stereospecificity and chemoselectivity. Table 3: Stereospecific, catalytic aminocarbonylation of (S)-1 with 18 8 and 28 8 amines and ammonium carbamate. [a] [a] Yields of isolated product are shown. Enantiospecificity (es) = (ee product /ee substrate ) 100 %, determined by chiral HPLC analysis.Scheme 1. Plausiblec atalyticc ycle for the catalytic stereospecific aminocarbonylation.

Metal‐catalyzed aminocarbonylation is a standard approach for installing amide functionality in chemical synthesis. Despite broad application of this transformation using aryl or vinyl electrophiles, there are few examples involving unactivated aliphatic substrates. Furthermore, there are no stereocontrolled aminocarbonylations of alkyl electrophiles known. Herein, we report a stereospecific aminocarbonylation of unactivated alkyl tosylates for the synthesis of enantioenriched amides. This cobalt‐catalyzed transformation uses a remarkably broad range of amines and proceeds with excellent stereospecificity and chemoselectivity.

No abstract