Visible light-induced direct conversion of aldehydes into nitriles in aqueous medium using Co@g-C3N4 as photocatalyst

Verma, Fooleswar; Shukla, Prashant; Bhardiya, Smita R.; Singh, Manorama; Rai, Ankita; Vijai, K.

doi:10.1016/j.catcom.2018.10.031

Cited by 34 publications

(21 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As the oxime is not converted to the final product in the absence of light (Figure 1 d), a following photocatalytic cycle is proposed (Figure 2, Cycle A′). Here, the oxime ( VII ) is oxidised to VIII ⋅ + via reductive quenching [7e] of PC‐4 + * followed by elimination of water to give intermediate IX . + .…”

Section: Resultsmentioning

confidence: 99%

“…Yet, this method employs toxic cyanide as stochiometric reagent, which can be a drawback, espcially in a bulk‐scale synthesis. Besides the use of a toxic cyanide source, a few photochemical methods for the synthesis of nitriles have been developed using a greener ammonium salt [7d,e, 14a] . These include the conversion of aldehydes to nitriles using a ruthenium photocatalyst with ammonium persulfate as nitrogen source (Scheme 1 A) [7d] or a heterogeneous Co@g‐C 3 N 4 photocatalyst together with NH 2 OH⋅HCl reported by the Rai group (Scheme 1 B).…”

Section: Introductionmentioning

confidence: 99%

“…These include the conversion of aldehydes to nitriles using a ruthenium photocatalyst with ammonium persulfate as nitrogen source (Scheme 1 A) [7d] or a heterogeneous Co@g‐C 3 N 4 photocatalyst together with NH 2 OH⋅HCl reported by the Rai group (Scheme 1 B). [7e] Another interesting transformation in this regard is the functionalization of styrenes to N‐hydroxybenzimidoyl cyanides (Scheme 1 C). [14a] Most photocatalytic methods furnishing nitriles in absence of cyanide use pre‐functionalized starting materials.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Visible‐Light‐Promoted Metal‐Free Synthesis of (Hetero)Aromatic Nitriles from C(sp³)−H Bonds**

2020

View full text Add to dashboard Cite

The metal-free activation of C(sp 3)-H bonds to valueadded products is of paramount importance in organic synthesis. Herein, we report the use of the commercially available organic dye 2,4,6-triphenylpyrylium tetrafluoroborate (TPP) for the conversion of methylarenes to the corresponding aryl nitriles via a photocatalytic process. Applying this methodology, a variety of cyanobenzenes have been synthesized in good to excellent yield under metal-and cyanide-free conditions. We demonstrate the scope of the method with over 50 examples including late-stage functionalization of drug molecules (celecoxib) and complex structures such as L-menthol, amino acids and cholesterol derivatives. Further, the presented synthetic protocol is applicable for gram-scale reactions. In addition to methylarenes, selected examples for the cyanation of aldehydes, alcohols and oximes are demonstrated as well. Detailed mechanistic investigations have been carried out using time-resolved luminescence quenching studies, control experiments and NMR spectroscopy as well as kinetic studies, all supporting the proposed catalytic cycle.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Visible‐Light‐Promoted Metal‐Free Synthesis of (Hetero)Aromatic Nitriles from C(sp³)−H Bonds**

2020

View full text Add to dashboard Cite

show abstract

“…Regardless of the above-mentioned organic conversion reactions, g-C 3 N 4 -based catalysts can be also applied to other types of transformation, including synthesis of aryl ketones, , esterification reactions, and so on. , The efficient conversion of these reactions fully demonstrates the importance of g-C 3 N 4 -based catalysts in organic synthetic chemistry.…”

Section: Applications Of G-c3n4-based Materialsmentioning

confidence: 99%

Graphitic Carbon Nitride-Based Photocatalytic Materials: Preparation Strategy and Application

Wang

et al. 2020

ACS Sustainable Chem. Eng.

123

View full text Add to dashboard Cite

Among various kinds of photocatalytic semiconductors, graphitic carbon nitride (g-C 3 N 4 )-based photocatalysts have become the most attractive "celebrity" because of their stable chemical properties, appropriate band structure, and facile synthesis. Here, we provide a systematic review of g-C 3 N 4based photocatalytic materials based on the latest related research progress. The design ideas and preparation methods of g-C 3 N 4based photocatalysts are summarized, including morphology control of a three-dimensional structure, active site engineering, defect/vacancy engineering, and interface engineering. In addition, the typical applications of g-C 3 N 4 -based photocatalysts are also discussed in detail, involving water splitting (overall water splitting, H 2 evolution, O 2 evolution), organic transformation reactions (oxidation reaction, reduction reaction, coupling reaction), and degradation of organic pollutants. This perspective ends with a summary and perspectives on facing the challenges and directions of future development in this research field.

show abstract

“…1b, 1c The nitrile moiety is an essential functional group in various drugs and bioactive compounds, 7 as well as an important building block for the preparation of fine and bulk chemicals, such as amines, carboxylic acids, amides and esters. 8 In conventional approaches, nitriles have been synthesized using the Sandmeyer reaction, 9 Rosenmundvon Braun reaction 10 and halide/CN exchange. 11 Further, transition-metal and photoredox catalyzed ammoxidations of aldehydes have been reported.…”

Section: Introductionmentioning

confidence: 99%

Visible-Light-Promoted Metal-Free Ammoxidation of C(sp3)-H bonds

Murugesan¹,

Donabauer²,

Koenig³

2020

Preprint

View full text Add to dashboard Cite

The metal-free activation of C(<i>sp</i><sup>3</sup>)-H bonds to value-added products is of paramount importance in organic synthesis. Herein, we report the use of the commercially available organic dye 2,4,6-triphenylpyrylium tetrafluoroborate (TPP) for the conversion of methylarenes to the corresponding aryl nitriles via a photo process. Applying this methodology, a variety of cyanobenzenes have been synthesized in good to excellent yield under metal- and cyanide-free conditions. We demonstrate the scope of the method with over 50 examples including late-stage functionalization of drug molecules (celecoxib) and complex structures such as L-menthol, amino acids and cholesterol derivatives. Further, the presented synthetic protocol is applicable for gram-scale reactions. In addition to methylarenes, selected examples for the cyanation of aldehydes, alcohols and oximes are demonstrated as well. Detailed mechanistic investigations have been carried out using time-resolved luminescence quenching studies, control experiments and NMR‑ spectroscopic as well as kinetic studies, all supporting the proposed catalytic cycle.

show abstract

Visible light-induced direct conversion of aldehydes into nitriles in aqueous medium using Co@g-C3N4 as photocatalyst

Cited by 34 publications

References 33 publications

Visible‐Light‐Promoted Metal‐Free Synthesis of (Hetero)Aromatic Nitriles from C(sp³)−H Bonds**

Visible‐Light‐Promoted Metal‐Free Synthesis of (Hetero)Aromatic Nitriles from C(sp³)−H Bonds**

Graphitic Carbon Nitride-Based Photocatalytic Materials: Preparation Strategy and Application

Visible-Light-Promoted Metal-Free Ammoxidation of C(sp3)-H bonds

Contact Info

Product

Resources

About

Visible light-induced direct conversion of aldehydes into nitriles in aqueous medium using Co@g-C3N4 as photocatalyst

Cited by 34 publications

References 33 publications

Visible‐Light‐Promoted Metal‐Free Synthesis of (Hetero)Aromatic Nitriles from C(sp3)−H Bonds**

Visible‐Light‐Promoted Metal‐Free Synthesis of (Hetero)Aromatic Nitriles from C(sp3)−H Bonds**

Graphitic Carbon Nitride-Based Photocatalytic Materials: Preparation Strategy and Application

Visible-Light-Promoted Metal-Free Ammoxidation of C(sp3)-H bonds

Contact Info

Product

Resources

About

Visible‐Light‐Promoted Metal‐Free Synthesis of (Hetero)Aromatic Nitriles from C(sp³)−H Bonds**

Visible‐Light‐Promoted Metal‐Free Synthesis of (Hetero)Aromatic Nitriles from C(sp³)−H Bonds**