Direct C–F Bond Formation Using Photoredox Catalysis

Rueda‐Becerril, Montserrat; Mahé, Olivier; Drouin, Myriam; Majewski, Marek B.; West, Julian G.; Wolf, Michael O.; Sammis, Glenn M.; Paquin, Jean‐François

doi:10.1021/ja412083f

Cited by 225 publications

(104 citation statements)

References 52 publications

Supporting

Mentioning

100

Contrasting

Unclassified

Order By: Relevance

“…Photoredox catalysis has been utilized to implement decarboxylative functionalizations, including additions to arenes 39–42 and alkenes, 43–50 as well as decarboxylative fluorinations 51–53 and decarboxylation of keto carboxylic acids to form ketones. 54 Wallentin and co-workers recently reported a photoredox method for the hydrodecarboxylation of stabilized carboxylic acids, such as protected amino acid derivatives, and phenyl acetic acid derivatives using a similar catalyst system to our own; however, aliphatic carboxylic acids were not found to be viable substrates using this method.…”

Section: Introductionmentioning

confidence: 99%

Hydrodecarboxylation of Carboxylic and Malonic Acid Derivatives via Organic Photoredox Catalysis: Substrate Scope and Mechanistic Insight

2015

View full text Add to dashboard Cite

A direct, catalytic hydrodecarboxylation of primary, secondary, and tertiary carboxylic acids is reported. The catalytic system consists of a Fukuzumi acridinium photooxidant with phenyldisulfide acting as a redox-active cocatalyst. Substoichiometric quantities of Hünig’s base are used to reveal the carboxylate. Use of trifluoroethanol as a solvent allowed for significant improvements in substrate compatibilities, as the method reported is not limited to carboxylic acids bearing α heteroatoms or phenyl substitution. This method has been applied to the direct double decarboxylation of malonic acid derivatives, which allows for the convenient use of dimethyl malonate as a methylene synthon. Kinetic analysis of the reaction is presented showing a lack of a kinetic isotope effect when generating deuterothiophenol in situ as a hydrogen atom donor. Further kinetic analysis demonstrated first-order kinetics with respect to the carboxylate, while the reaction is zero-order in acridinium catalyst, consistent with another finding suggesting the reaction is light limiting and carboxylate oxidation is likely turnover limiting. Stern–Volmer analysis was carried out in order to determine the efficiency for the carboxylates to quench the acridinium excited state.

show abstract

Section: Introductionmentioning

confidence: 99%

Hydrodecarboxylation of Carboxylic and Malonic Acid Derivatives via Organic Photoredox Catalysis: Substrate Scope and Mechanistic Insight

2015

View full text Add to dashboard Cite

show abstract

“…33) [62]. The authors show that a ruthenium bipyridine catalyst is oxidized by Selectfluor after absorption of light.…”

Section: Fluorination Of C-h Bondsmentioning

confidence: 99%

Transition Metal-Mediated and Metal-Catalyzed Carbon–Fluorine Bond Formation

Campbell

Hoover

Ritter

2014

Topics in Organometallic Chemistry

View full text Add to dashboard Cite

The development of new C-F bond forming reactions from organotransition metal complexes has played a key role in advancing the field of fluorination chemistry and has allowed for improved access to fluorinated organic molecules of interest in medicine, materials, and agrochemicals. In this review, we describe the development of transition metal-mediated and metal-catalyzed fluorination methods over the past decade. Special attention is paid to the variety of organometallic mechanisms by which C-F bond formation can occur and the strengths and limitations of different approaches.

show abstract

“…Organocatalysis refers to the use of small organic molecules to catalyse organic transformations. During the last decades, organocatalysis has been included among the most important and successful concepts in asymmetric catalysis and it has been used for the enantioselective construction of C-C, C-N, C-O, C-S, C-P and C-halide bonds [15][16][17][18][19][20]. Furthermore, this new branch experienced a boom in the first eight years from its advent.…”

Section: Definition and Origins Of Organocatalysismentioning

confidence: 99%

Organocatalysts for enantioselective synthesis of fine chemicals: definitions, trends and developments

Federsel¹

2014

ScienceOpen Research

View full text Add to dashboard Cite

Organocatalysis, that is the use of small organic molecules to catalyse organic transformations, has been included among the most successful concepts in asymmetric catalysis and it has been used for the enantioselective construction of C-C, C-N, C-O, C-S, C-P, and C-halide bonds. Since the seminal works in early 2000, the scientific community has been paying an ever-growing attention to the use of organocatalysts for the synthesis, with high yields and remarkable stereoselectivities, of optically active fine chemicals of interest for the pharmaceutical industry. A brief overview is here presented about the two main classes of substrate activation by the catalyst: covalent organocatalysis and non-covalent organocatalysis, with a more stringent focus on some recent outcomes in the field of the latter and of hydrogen-bond-based catalysis. Finally, some successful examples of heterogenisation of organocatalysts are also discussed, in the view of a potential industrial exploitation.

show abstract

Direct C–F Bond Formation Using Photoredox Catalysis

Cited by 225 publications

References 52 publications

Hydrodecarboxylation of Carboxylic and Malonic Acid Derivatives via Organic Photoredox Catalysis: Substrate Scope and Mechanistic Insight

Hydrodecarboxylation of Carboxylic and Malonic Acid Derivatives via Organic Photoredox Catalysis: Substrate Scope and Mechanistic Insight

Transition Metal-Mediated and Metal-Catalyzed Carbon–Fluorine Bond Formation

Organocatalysts for enantioselective synthesis of fine chemicals: definitions, trends and developments

Contact Info

Product

Resources

About