Ni-Catalyzed Direct Carboxylation of Benzyl Halides with CO<sub>2</sub>

“…One clever example is from Martin and coworkers, which transformed benzylic halides to the corresponding phenylacetic acids using carbon dioxide as the carbon source. 43 Subsequently, this methodology was extended to aryl and benzylic pivalates to synthesize benzoates and phenylacetic acids. 44 Additionally, the activation of benzylic ammonium salts has recently been demonstrated.…”

Section: Cross-couplingmentioning

confidence: 99%

Recent advances in homogeneous nickel catalysis

Tasker

Standley

Jamison

2014

Nature

1,944

1,098

View full text Add to dashboard Cite

Preface The field of nickel catalysis has made tremendous advances in the past decade. There are several key properties of nickel that have allowed for a broad range of innovative reaction development, such as facile oxidative addition and ready access to multiple oxidation states. In recent years, these properties have been increasingly understood and leveraged to perform transformations long considered exceptionally challenging. Herein, we discuss some of the most recent and significant developments in homogeneous nickel catalysis with an emphasis on both synthetic outcome and mechanism.

show abstract

“…Driven by the prevalence of phenylacetic acids in molecules that display significant biological activities such as vancomycin, carbenicillin, or ibuprofen, among others, 6 our group described a Ni-catalyzed reductive carboxylation of primary, secondary, or even tertiary benzyl halides with CO 2 at atmospheric pressure and Zn dust as reductant (Scheme 5). 22 The role of additives was found to be critical, with MgCl 2 and TBAI providing the best results when dealing with the coupling of primary or secondary/tertiary benzyl halides, respectively. Under these conditions, a variety of functional groups could be accommodated, including alkenes, ketones, esters, or even aryl halides, thus leaving ample room for orthogonal modifications.…”

Section: Direct Catalytic Carboxylation Of Organic Halides With Co2mentioning

confidence: 98%

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

et al. 2016

Self Cite

View full text Add to dashboard Cite

The recent years have witnessed the development of metal-catalyzed reductive carboxylation of organic (pseudo)halides with CO2 as C1 source, representing potential powerful alternatives to existing methodologies for preparing carboxylic acids, privileged motifs in a myriad of pharmaceuticals and molecules displaying significant biological properties. While originally visualized as exotic cross-coupling reactions, a close look into the literature data indicates that these processes have become a fertile ground, allowing for the utilization of a variety of coupling partners, even with particularly challenging substrate combinations. As for other related cross-electrophile scenarios, the vast majority of reductive carboxylation of organic (pseudo)halides are characterized by their simplicity, mild conditions, and a broad functional group compatibility, suggesting that these processes could be implemented in late-stage diversification. This perspective describes the evolution of metal-catalyzed reductive carboxylation of organic (pseudo)halides from its inception in the pioneering stoichiometric work of Osakada to the present. Specific emphasis is devoted to the reactivity of these coupling processes, with substrates ranging from aryl-, vinyl-, benzyl- to unactivated alkyl (pseudo)halides. Despite the impressive advances realized, a comprehensive study detailing the mechanistic intricacies of these processes is still lacking. Some recent empirical evidence reveal an intriguing dichotomy exerted by the substitution pattern on the ligands utilized; still, however, some elementary steps within the catalytic cycle of these reactions remain speculative, in many instances invoking a canonical cross-coupling process. Although tentative, we anticipate that these processes might fall into more than one distinct mechanistic category depending on the substrate utilized, suggesting that investigations aimed at unraveling the mechanistic underpinnings of these processes will likely bring new and innovative research grounds in this vibrant area of expertise.

show abstract

Ni-Catalyzed Direct Carboxylation of Benzyl Halides with CO₂

Cited by 274 publications

References 49 publications

Making C–C Bonds from Carbon Dioxide via Transition-Metal Catalysis

Making C–C Bonds from Carbon Dioxide via Transition-Metal Catalysis

Recent advances in homogeneous nickel catalysis

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

Contact Info

Product

Resources

About

Ni-Catalyzed Direct Carboxylation of Benzyl Halides with CO2

Cited by 274 publications

References 49 publications

Making C–C Bonds from Carbon Dioxide via Transition-Metal Catalysis

Making C–C Bonds from Carbon Dioxide via Transition-Metal Catalysis

Recent advances in homogeneous nickel catalysis

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO2

Contact Info

Product

Resources

About

Ni-Catalyzed Direct Carboxylation of Benzyl Halides with CO₂

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂