Catalyst- and solvent-free<i>ipso</i>-hydroxylation of arylboronic acids to phenols

Yang, Xiulin; Jiang, Xulu; Wang, Weitao; Yang, Qi; Ma, Yangmin; Wang, Kuan

doi:10.1039/c9ra07201b

Cited by 18 publications

(7 citation statements)

References 39 publications

(28 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The corresponding Δ E f values under dark and light conditions are ≈70 and ≈91 meV, respectively. As the work function of the QDs (3.39 eV) [ 33 ] is smaller than that of graphene (4.5 eV), [ 34 ] the introduction of the QDs causes the Fermi level of the graphene to move upward. [ 35 ] This increases the gap between the Fermi levels of the 3D‐Gr and 2D‐Gr.…”

Section: Resultsmentioning

confidence: 99%

Intact Vertical 3D–0D–2D Carbon‐Based p–n Junctions for Use in High‐Performance Photodetectors

Feng

Liu

et al. 2021

Advanced Optical Materials

View full text Add to dashboard Cite

Ultrathin 2D graphene (2D‐Gr) sheets have inherently weak absorption characteristics (only 2.3%). Pristine‐graphene‐based photodetectors therefore have short carrier lifetimes and small Schottky barriers that severely restrict their practical application. In this work, chemical vapor deposition (CVD) and dynamic plasma‐assisted CVD (PACVD) are used to grow vertical p–n junctions in situ, which can then be used to form novel near‐infrared photodetectors. The directly formed vertical heterostructures feature 0D C3N quantum dots (QDs) in the middle position which acts as nucleation seeds to directly and rapidly grow 3D graphene (3D‐Gr) structures that act as the n‐type region. The bottom layer consists of a single‐crystal 2D‐Gr film that forms the p‐type region. The large built‐in electric field at the interface of the depletion region of the 3D‐Gr/2D‐Gr vertical p–n junction leads to the rapid separation of any photogenerated electron–hole pairs. Thus, the photodetector exhibits an excellent responsivity of 2.98 × 107 A W−1 and a detectivity of 1.04 × 1013 cm Hz1/2 W−1 at a wavelength of 1550 nm. The response speed of the photodetector is ultrafast and exceeds that of other vertical/lateral p–n‐junction‐based photodetectors. Its speed is ascribed to the synergism that exists between the C3N QDs and 3D‐Gr due to their unique electron distributions and structural distortions. The research paves the way for a novel class of high‐performance graphene‐based photodetectors with hybrid architecture.

show abstract

Section: Resultsmentioning

confidence: 99%

Intact Vertical 3D–0D–2D Carbon‐Based p–n Junctions for Use in High‐Performance Photodetectors

Feng

Liu

et al. 2021

Advanced Optical Materials

View full text Add to dashboard Cite

show abstract

“…After Int w ‐2 releases B(OH) 3 , a phenyl complex PhRhP ( Int w ‐3 ) is formed, which is similar to our previous work. [ 34 ] Next, the hydroxymethylation step ( Int w ‐3 → Int w ‐4 ) takes place through TS w ‐2 with a very high free energy barrier of 68.6 kcal mol −1 for producing the intermediate Int w ‐4 , indicating that the H 2 O complex pathway is severely unlikely to occur. Obviously, the aromatic complex pathway is more favorable Rh‐catalyzed pathway in the hydroxymethylation of PBA and HCHO with RhCl(PPh 3 ) 3 .…”

Section: Resultsmentioning

confidence: 99%

Experimental and density functional theory studies on hydroxymethylation of phenylboronic acids with paraformaldehyde over a RhPPh₃ catalyst

Wang

Lan

et al. 2020

Applied Organom Chemis

Self Cite

View full text Add to dashboard Cite

The synthesis of benzyl alcohols (BAs) is highly vital for their wide applications in organic synthesis and pharmaceuticals. Herein, BAs was efficiently synthesized via hydroxymethylation of phenylboronic acids (PBAs) and paraformaldehyde over a simple RhPPh3 catalyst combined with an inorganic base (NaOH). A variety of BAs with the groups of CH3−, CH3O−, Cl−, Br−, and so on were obtained with moderate to good yields, indicating that the protocol had a good universality. Density functional theory (DFT) calculations proposed the Hayashi‐type arylation mechanism involved the arylation step of PBA and Rh(OH)(PPh3)2 catalyst to form Rh(I)‐bound aryl intermediates and the hydrolysis step of Rh(I)‐bound aryl intermediates and HCHO to generate BA product (the rate‐determining step). The present route provides a valuable and direct method for the synthesis of BAs and expands the application range of paraformaldehyde.

show abstract

“…In direct comparison, the ipso ‐hydroxylation of boronic acids and their esters poses an attractive alternative, as these starting materials are widely available due to their wide‐spread application in Suzuki–Miyaura cross‐coupling reactions [7–9] . Arylboronic acids can be converted into the corresponding phenols by reaction with alkaline hydrogen peroxide (or it's adducts), [10,11] sodium perborate, [12] molecular oxygen, [13] N ‐oxides, [14] or hypervalent iodine compounds [15] . Similarly, the products of the hydroboration of alkenes can be converted to the respective alcohols [10,11,15–18] .…”

Section: Introductionmentioning

confidence: 99%

The Oxidation of Organo‐Boron Compounds Using Electrochemically Generated Peroxodicarbonate

et al. 2023

View full text Add to dashboard Cite

Peroxodicarbonate represents a green and largely underexplored oxidizer generated electrochemically from aqueous carbonate solutions. Through state-of-the-art electrolyzer technology, highly concentrated solutions have now become accessible. These were successfully employed as green oxidizer in deborolative hydroxylations. A plethora of phenols and alcohols have thus been synthesized in up to 99 % from organoboron compounds using only green and non-toxic solvents. This transformation was successfully scaled-up to multi-gram batch sizes.

show abstract

Catalyst- and solvent-freeipso-hydroxylation of arylboronic acids to phenols

Abstract: A catalyst-free method for the hydroxylation of arylboronic acids to form the corresponding phenols with sodium perborate as the oxidant was developed using water as the solvent or solvent free condition.

Cited by 18 publications

References 39 publications

Intact Vertical 3D–0D–2D Carbon‐Based p–n Junctions for Use in High‐Performance Photodetectors

Intact Vertical 3D–0D–2D Carbon‐Based p–n Junctions for Use in High‐Performance Photodetectors

Experimental and density functional theory studies on hydroxymethylation of phenylboronic acids with paraformaldehyde over a RhPPh₃ catalyst

The Oxidation of Organo‐Boron Compounds Using Electrochemically Generated Peroxodicarbonate

Contact Info

Product

Resources

About

Catalyst- and solvent-freeipso-hydroxylation of arylboronic acids to phenols

Abstract: A catalyst-free method for the hydroxylation of arylboronic acids to form the corresponding phenols with sodium perborate as the oxidant was developed using water as the solvent or solvent free condition.

Cited by 18 publications

References 39 publications

Intact Vertical 3D–0D–2D Carbon‐Based p–n Junctions for Use in High‐Performance Photodetectors

Intact Vertical 3D–0D–2D Carbon‐Based p–n Junctions for Use in High‐Performance Photodetectors

Experimental and density functional theory studies on hydroxymethylation of phenylboronic acids with paraformaldehyde over a RhPPh3 catalyst

The Oxidation of Organo‐Boron Compounds Using Electrochemically Generated Peroxodicarbonate

Contact Info

Product

Resources

About

Experimental and density functional theory studies on hydroxymethylation of phenylboronic acids with paraformaldehyde over a RhPPh₃ catalyst