Selective alcohol oxidation catalysed BY FeCl3 /novel glycine functionalised IONIC liquid

Article abstract of DOI:10.1016/j.jics.2021.100099

An effective and eco-friendly technique were designated for quick alcohol oxidation by glycine functionalised imidazolium ionic liquids in presence of FeCl₃ at ambient-temperature. No over the primary alcohols oxidation to carbonyl compounds was observed in presence of this FeCl₃/[Gmim]Cl. These benefits of the catalyst resulted mainly from the circumstance with alcohols-H₂O₂, and the Fe³⁺ was coordinated by the immobilized IL to permitted both reactants to access the active sites of the catalyst effectively. The catalyst recycled nine times without loss of activity.

Full text of DOI:10.1016/j.jics.2021.100099

Journal of the Indian Chemical Society 98 (2021) 100099
Contents lists available at ScienceDirect
Journal of the Indian Chemical Society
journal homepage: www.editorialmanager.com/JINCS/default.aspx
Selective alcohol oxidation catalysed BY FeCl /novel glycine functionalised
3
IONIC liquid
a
b
a
Ganesh Gopalsamy Selvaraj , Uthayanila Selvarasu , Deepa Manickam ,
Parasuraman Karthikeyan a
,*
a
PG and Research Department of Chemistry, Pachaiyappas College Campus, University of Madras Chennai, 600 030, India
Department of Chemistry, Pachaiyappas College for Women Campus, University of Madras, Kanchipuram, 631501, Tamilnadu, India
b
A R T I C L E I N F O
A B S T R A C T
Keywords:
Carbonyl compound
Iron
Green chemistry
Peroxide
Alcohol
An effective and eco-friendly technique were designated for quick alcohol oxidation by glycine functionalised
imidazolium ionic liquids in presence of FeCl
carbonyl compounds was observed in presence of this FeCl
mainly from the circumstance with alcohols-H
3
at ambient-temperature. No over the primary alcohols oxidation to
3
/[Gmim]Cl. These benefits of the catalyst resulted
, and the Fe was coordinated by the immobilized IL to
3þ
O
2 2
permitted both reactants to access the active sites of the catalyst effectively. The catalyst recycled nine times
without loss of activity.
1. Introduction
substantial amount of care in the topical literature as a powerful transi-
tion metal catalysed reaction. Due to its low cost, ready abundance, and
Conversion Alcohol into carbonyl compounds is one of the vibrant
low toxicity, iron is an ideal metal catalyst for large scale synthesis. This
growth of iron-catalysed methods, however, is still in its beginning. The
current efforts to employ iron as a catalyst for Kumada couplings,
hydrogenative reductions, friedel-crafts reactions and dihydroxylations
functional group transformations in organic synthesis [1–4]. However,
those compounds found a significant group of molecules in synthetic
chemistry and also essential constituent of dyes, fragrances, pharma-
ceuticals, industrially important chemicals, and natural products [5–8].
There are several diverse schemes that accomplish this important func-
tional group conversion [9–11].
provided
a
direct evaluation among state-of-the-art transition
metal-catalysed reactions, environmentally friendly and sustainable
metal [1–4,39–42,56].
Moreover, etiquettes based on O
attractive for cheap and eagerly existing oxidants. Accordingly,
numerous studies have been reported for the alcohol oxidation with O or
catalysed by metal complexes such as Ruthenium [15–17], Palla-
dium [18–20], Cobalt [21–24], Osmium [25,26], Copper [27,28] and
heterogeneous catalysts like metal catalysts besides supported catalysts,
with mesoporous materials, zeolite, polymer-supported catalysts
2
, air or H
2
O
2
[12–14] are mainly
This recent years, Caselli et al. [43] initiated non-heme complexes
suitable for the selective oxidation of primary and secondary alcohols to
the corresponding ketones. However, Iskra and Mozina [44] efficiently
accomplished selective oxidation of secondary catalysed by iron (III)
chloride. Sato and co-worker [45] testified an efficient catalytic oxida-
tion of alcohols with hydrogen peroxide using mixed picolinate and
quinaldinate iron (III) complexes. Liang et al. [46] developed a simple
chemical model for aerobic oxidation of primary alcohols to the alde-
hydes catalysed by iron chloride/4-acetamido-TEMPO/sodium nitrite.
Biswas et al. [47] studied primary and secondary alcohols to carbonyl
compounds in the presence dinuclear iron complexes as catalysts using
hydrogen peroxide as primary oxidant.
2
2 2
H O
[
29–31], tungsten systems like tungstic acid [32–35], quaternary
ammoniumtetrakis (diperoxotungsto) phosphates [32–35] sodium
tungstate [(n-C N] Cl, sodium tungstate and quaternary ammonium
4 9 4
H )
hydrogen sulfate [32–35].
However, in spite of this exhaustive research method, alcohol
oxidation is still far being ideal from the green chemistry point of view
and needs to improvement [36–38]. There is only a limited report of
using cheap and less toxic iron catalysts for the alcohol oxidation to
carbonyls so far [39–42]. Nowadays, Schiff-iron has established a
Over all the outlines afford good yield, but some have problematics
issue such as extensive work-up method, severe reaction conditions
(organic co-solvents) and require absolutely dry and inert media. To our
3
best info, there is no report of with the FeCl /glycine functionalised ionic
*
Corresponding author.
E-mail address: pkarthikeyan99@gmail.com (P. Karthikeyan).
https://doi.org/10.1016/j.jics.2021.100099
Received 25 May 2021; Received in revised form 18 June 2021; Accepted 5 July 2021
019-4522/© 2021 Indian Chemical Society. Published by Elsevier B.V. All rights reserved.
0

G. Gopalsamy Selvaraj et al.
Journal of the Indian Chemical Society 98 (2021) 100099
3
Scheme 1. Oxidation of alcohols catalysed by FeCl /[Gmim]Cl.
Table 1
l-1H-imidazole-3-ium chloride) [Gmim]Cl. The solvent (acetonitrile)
was removed under reduced pressure at 80 OC. Then the residue was
a
Optimization of oxidation reaction. .
Entry
Different Solvent
Time (hrs)
Conv. (%)b
Yield (%)c
mixed with 50 mL water and extracted with ethyl acetate (3 ꢀ 5 mL).
Blankd
Toluene
DCM
EtOAc
DME
THF
Further, the water phase was evaporated under reduced pressure at 80
1
2
3
4
5
6
7
8
9
24
24
24
24
24
24
24
24
24
10
10
10
15
3
2
O
31
26
18
22
28
34
40
20
96
97
96
96
96
95
28
24
17
20
27
33
37
19
94
95
94
94
94
92
C until the mass of the residue did not change.
2.3. Typical oxidation procedure
MeCN
3
To a mixture of FeCl (0.25 mol%), [Gmim]Cl (1 mL), benzyl alcohol
CHCl
DMF
3
(10 mmol) and H
O
(1.2 mmol) was slowly added. The resulting reac-
2
2
ꢁ
tion mixture was stirred at room (25 C) temperature for 10 min. After
completion of the reaction, ether was added (3 ꢀ 5 mL) to separate the
product from catalyst. The organic layer was concentrated and purified
by column chromatography to give the benzaldehyde.
e
10
11
12
13
14
15
[Gmim]Cl
[Gmim]Cl
[Gmim]Cl
[Gmim]Cl
[Gmim]Cl
[Gmim]Cl
e,f
e,g
e,h
e,i
10
10
e,j
3
. Results and discussion
a
Reaction condition: Benzyl alcohol (1 mmol), Hydrogen perxide (1.2 mmol),
O
FeCl
3
(0.25 mol%), [Gmim]Cl (1 mL) at 25 C for 10 min.
To get information on the optimal catalyst conditions, we carried out
intensive examinations to define the suitable solvent for this benzyl
alcohol oxidation reaction. According to publications from Rani and Bhat
b
Based on GC.
Isolated yield by flash chromatography.
Absence of catalyst.
Time in mints.
Increases of conc. of FeCl
Increases of conc. of H
Time to increase from 10 to 15 mints.
Temperature (30 C).
c
d
e
f
[
52], Hergovich and Speier [53] and Renhua Liu [54] polar, non-polar
solvents tend to give the best results for the oxidation reaction, while
Ma [55] obtained high-activity of catalysts in DCE solvent. Among the
previous reports, alcohol oxidation in absence polar and non-polar sol-
vents was the most productive (Table 1, entries 2–9). This may be due to
3
from 0.25 to 0.5 mol%.
as the oxidant from 10% to 30%.
g
h
i
2
O
2
ꢁ
ꢁ
j
the easy coordination of FeCl
3
with organic co-solvents. Our goal was to
Temperature (20 C).
employ FeCl under ligand, organic solvent-free conditions to effect the
3
alcohol oxidation reaction on a recyclable basis. Amino acid functional-
ised ionic liquids were chosen because of their recyclability and reus-
ability. The products can be easily separated from the FeCl catalysts
3
dissolved in ionic liquids by simple extraction with normal organic sol-
vents. We reasoned that if the ligand has an imidazole moiety, it will have
high solubility in ionic liquids having the imidazole skeleton.
liquids, as catalyst for oxidation of alcohols. This prompted us to study
the possibility of the oxidation of alcohols to carbonyl compounds in the
3 2 2
presence of FeCl /[Gmim]Cl under mild conditions using H O as
oxidant (Scheme 1).
2. Experimental
Subsequent, the combination of glycine functionalised ionic liquids
3
with FeCl was tried as the catalyst for the oxidation reaction. As shown
2
.1. Materials and methods
in (Table 1, entry 10) the catalytic oxidation continued with mild con-
version of alcohol to aldehyde with satisfactory yield. Furthermore, ac-
cording to literature, Renhua Liu and co-workers obtained good yield in
the oxidation reaction of primary alcohols to the aldehydes using iron
All solvents and chemicals were commercially available and used
1
without further purification unless otherwise stated. The H NMR spectra
were recorded on a Bruker 500 MHz using CDCl as the solvent and mass
3
O
chloride (0.25 mmol) stirred at 50 C and oxygen pressure of 0.4 MPa for
spectra were recorded on JEOL GC MATE II HRMS (EI) spectrometer. FT-
IR was recorded on AVATRA 330 spectrometer with DTGS detector.
Column chromatography was performed on silica gel (200–300 mesh).
Analytical thin-layer chromatography (TLC) was carried out on pre-
coated silica gel GF-254 plates.
3 3 2
03–23 h [54]. Using Fe(NO ) ⋅9H O in the 10 mol%, Ma et al. observed
acceptable rate in the oxidation [55]. Among the previous reports,
increasing the quantity of the catalyst can improve the reaction yield and
shorten reaction time. However, the influences of the amount of FeCl
and H were also examined. It is renowned that increasing increase
from 0.25 to 0.5 mol% the quantity of FeCl led to improved yield
(Table 1, entry 11). However, the quantity of H increased from 10%
3
2 2
O
3
2
.2. Synthesis of [Gmim]Cl
2 2
O
to 30%, the reaction was not influenced to greater extent (Table 1, entry
12). It is found that the alcohol oxidation was very fast in 10 min and
nearly approached the chemical equilibrium subsequently 15 min
(Table 1, entry 13). However, temperature also plays a significant role in
The catalyst [Gmim]Cl was synthesized and reported [50,51]. First,
chloroglycine (0.01 mol) reacted with N-Methylimidazole (0.11 mol) in
O
5
0 mL acetonitrile at 70 C for 24 h to generate chloroglycine ligand
O
modified by imidazole salt (3-(amino(carboxy)methyl)-1-methy
the model reaction. When we conducted the oxidation reaction at 30 C,
2

G. Gopalsamy Selvaraj et al.
Journal of the Indian Chemical Society 98 (2021) 100099
Table 2
Catalytic oxidation of primary alcohols Oxidation in the presence of FeCl
3
/[Gmim]Cla.
very high activity of the system [39–42].
One of the main objectives of green chemistry is to increase the life of
the resulting catalyst. We have completed an introductory study of the
Table 3
Recycling of FeCl
/[Gmim]Cl.a.
Conversion (%)b
3
Run
Yield (%)c
3
recycling productivity of FeCl /[Gmim]Cl using benzyl alcohol as model
1
2
3
4
5
6
7
8
9
96
96
96
96
95
95
94
94
94
94
94
93
93
93
93
92
92
91
substrate. The FeCl /[Gmim]Cl was disconnected from the reaction after
3
each trial by extraction with diethyl ether followed by ethyl acetate to
recover [Gmim]Cl. The excess solvent was removed by vacuum distilla-
tion sensibly before using it in the next cycle. The catalyst was recycled
nine times without conspicuous loss and activity (Table 3, entries 1–9).
4
. Conclusions
a
2 2 3
Reaction condition: benzyl alcohol (10 mmol), H O (12 mmol), FeCl (0.25
3
In summary, we have established the effective examples of FeCl /
Gmim]Cl procedure that have catalysed oxidation of various alcohols to
mol%), [Gmim]Cl (1 mL) at room temperature for 10 min.
[
b
Conversion by GC.
Isolated yield by flash chromatography.
the ketones and aldehydes in outstanding yields. The activity of several
alcohol oxidation in the currently testified catalytic systems is much
higher than that of other aerobic oxidations in ILs/ILs-transition metals,
even with lesser catalyst loading and devoid of any additive. Addition-
ally, Easy technique, broad substrate applicability, high yields, short
reaction times can be mentioned as advantages of this method. No sol-
vent vapors released and smallest wastage of reagents during the reaction
makes this as ‘green’ process.
c
there was no change in the yield (Table 1, entry 14) but in the case of
0 C decrease in the carbonyl compound (Table 1, entry 15).
O
2
Under the optimized conditions, the other alcohols oxidation was
studied (Table 2). The primary aromatic alcohols explored and provided
first-rate yields (Table 2, entries a-g). However, parallelly the oxidation
of benzyl alcohol gave good conversion and yield (85–96%) were found
over the alcohols attached electron-withdrawing and donating groups in
the aromatic ring, i.e., p-chloro, p-bromo, p-methoxyl, p-amino and p-
methyl benzyl alcohols (Table 2, entries b-h).
Declaration of competing interest
Interestingly, in contrast to B. Andrioletti, work [48] aliphatic alco-
hols were also oxidized to carbonyl compounds, with outstanding yield in
short duration (Table 2, entries i-k). Thus, we could achieve oxidation of
various aliphatic, alicyclic and aromatic alcohols to corresponding car-
bonyls without over oxidation under solvent free condition, in contrast to
Shannon S. Stahl co-works [49] which showed organic solvents were
necessary during the oxidation. The system gave well to quantitative
yields on oxidation of alcohol due to the effect of cation that facilitated
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
We great fully acknowledge the management of PC-Campus for
providing required facilities and SAIF (VIT-Vellore) for providing the
spectral data.
3þ
for the formation of catalytic complex with the Fe which resulted into a
3

G. Gopalsamy Selvaraj et al.
Journal of the Indian Chemical Society 98 (2021) 100099
Appendix A. Supplementary data
[23] Shi S, Liu M, Zhao L, Wang M, Chen C, Gao J, Xu J. Catalytic oxidation of alcohol to
carboxylic acid with a hydrophobic cobalt catalyst in hydrocarbon solvent. Chem.
Asian J. 2017;18:2404–9. https://doi.org/10.1002/asia.201700717.
Supplementary data to this article can be found online at https://do
i.org/10.1016/j.jics.2021.100099.
[
24] Reddy VG, Jampaiah D, Chalkidis A, Sabri YM, Mayes ELH, Bhargava SK. Highly
dispersed cobalt oxide nanoparticles on manganese oxide nanotubes for aerobic
oxidation of benzyl alcohol. Catal. Commun. 2019;130:105763. https://doi.org/
1
0.1016/j.catcom.2019.105763.
References
[25] Esteruelas MA, Obregon TG, Herrero J, Olivan M. Osmium-catalyzed oxidation of
primary alcohols with molecular oxygen. Organometallics 2011;30:6402–7.
https://doi.org/10.1021/om200684m.
[
1] Hao Z, Li Y, Ma Z, Han Z, Lin J, Lu GL. Trinuclear ruthenium carbonyl complexes
with salicylaldimine ligands as efficient catalysts for the oxidation of secondary
alcohols. J. Organomet. Chem. 2021;932:121647. https://doi.org/10.1016/
j.jorganchem.2020.121647.
[
26] Zahmakıran M, Akbayrak S, Kodaira T, Ozkar S. Osmium(0) nanoclusters stabilized
by zeolite framework; highly active catalyst in the aerobic oxidation of alcohols
under mild conditions. Dalton Trans. 2010;39:7521–7. https://doi.org/10.1039/
C003200J.
[
[
[
[
[
[
2] Jiang X, Liu J, Ma S. Iron-catalyzed aerobic oxidation of alcohols: lower cost and
improved selectivity. Org. Process Res. Dev. 2019;23:825–35. https://doi.org/
[
27] Nejad MJ, Salamatmanesh A, Heydari A. Copper (II) immobilized on magnetically
separable L-arginine-β-cyclodextrin ligand system as a robust and green catalyst for
direct oxidation of primary alcohols and benzyl halides to acids in neat conditions.
J. Organomet. Chem. 2020;911:121128. https://doi.org/10.1016/
j.jorganchem.2020.121128.
1
0.1021/acs.oprd.8b00374.
3] Urgoitia G, SanMartin R, Herrero MT, Dominguez E. Aerobic cleavage of alkenes
and alkynes into carbonyl and carboxyl compounds. ACS Catal. 2017;7:3050–60.
https://doi.org/10.1021/acscatal.6b03654.
4] Dai C, Zhang J, Huang C, Lei Z. Ionic liquids in selective oxidation: catalysts and
solvents. Chem. Rev. 2017;117:6929–83. https://doi.org/10.1021/
acs.chemrev.7b00030.
5] Holmes M, Schwartz LA, Krische MJ. Intermolecular metal-catalyzed reductive
coupling of dienes, allenes, and enynes with carbonyl compounds and imines.
Chem. Rev. 2018;118:6026–52. https://doi.org/10.1021/acs.chemrev.8b00213.
6] Cook AW, Waldie KM. Molecular electrocatalysts for alcohol oxidation: insights and
challenges for catalyst design. ACS Appl. Energy Mater. 2020;3:38–46. https://
doi.org/10.1021/acsaem.9b01820.
[
[
[
[
[
[
28] Vanoye L, Pablos M, de Bellefon C, Reguillon AF. Gas–liquid segmented flow
microfluidics for screening copper/TEMPO-catalyzed aerobic oxidation of primary
alcohols. Adv. Synth. Catal. 2015;357:739–46. https://doi.org/10.1002/
adsc.201400925.
29] Hu K, Tang J, Cao S, Zhang Q, Wang J, Ye Z. Tempo-functionalized aromatic
polymer as a highly active, Ph-responsive polymeric interfacial catalyst for alcohol
oxidation. J. Phys. Chem. C 2019;123:9066–73. https://doi.org/10.1021/
acs.jpcc.9b00467.
30] Karimi B, Mansouri F, Vali H. Minimizing the size of palladium nanoparticles
immobilized within the channels of ionic liquid-derived magnetically separable
heteroatom-doped mesoporous carbon for aerobic oxidation of alcohols. ACS Appl.
Nano Mater. 2020;3:10612–27. https://doi.org/10.1021/acsanm.0c01780.
31] Sharma M, Das B, Sharma M, Deka BK, Park YB, Bhargava SK, Bania KK. Pd/Cu-
Oxide nanoconjugate at zeolite-y crystallite crafting the mesoporous channels for
selective oxidation of benzyl-alcohols. ACS Appl. Mater. Interfaces 2017;9:
7] Salimi M, Zamanpour A. Ag nanoparticle immobilized on functionalized magnetic
3 4
hydrotalcite (Fe O /HT-SH-Ag) for clean oxidation of alcohols with TBHP. Inorg.
Chem. Commun. 2020;119:108081. https://doi.org/10.1016/
j.inoche.2020.108081.
[
[
8] Zhao JP, Hernandez WY, Zhou WJ, Yang Y, Vovk EI, Capron M, Ordomsky V.
Selective oxidation of alcohols to carbonyl compounds over small size colloidal Ru
nanoparticles. ChemCatChem 2019;12:238–47. https://doi.org/10.1002/
cctc.201901249.
9] Rafiee M, Konz ZM, Graaf MD, Koolman HF, Stahl SS. Electrochemical oxidation of
alcohols and aldehydes to carboxylic acids catalyzed by 4-acetamido-tempo: an
alternative to “anelli” and “pinnick” oxidations. ACS Catal. 2018;8:6738–44.
https://doi.org/10.1021/acscatal.8b01640.
3
5453–62. https://doi.org/10.1021/acsami.7b11086.
32] Sabaghi M, Aghajani Z, Najafi GR. Fabrication of a new heterogeneous tungstate-
based on the amino-functionalized metal-organic framework as an efficient catalyst
towards sonochemical oxidation of alcohols under green condition. J. Organomet.
Chem. 2020;925:121483. https://doi.org/10.1016/j.jorganchem.2020.121483.
33] Mohammadi M, Rezaei A, Khazaei A, Xuwei S, Huajun Z. Targeted development of
sustainable green catalysts for oxidation of alcohols via tungstate-decorated
multifunctional amphiphilic carbon quantum dots. ACS Appl. Mater. Interfaces
[
[
[
10] Hinzmann A, Stricker M, Busch J, Glinski S, Oike K, Groger H. Selective TEMPO-
oxidation of alcohols to aldehydes in alternative organic solvents. Eur. J. Org Chem.
2
019;11:33194–206. https://doi.org/10.1021/acsami.9b07961.
2
020;2020:2399–408. https://doi.org/10.1002/ejoc.201901365.
[
[
34] Moshofsky B, Mokari T. Length and diameter control of ultrathin nanowires of
substoichiometric tungsten oxide with insights into the growth mechanism. Chem.
Mater. 2013;25:1384–91. https://doi.org/10.1021/cm302015z.
35] Stadler IO, Rossell MD, Niederberger M. Co-operative formation of monolithic
tungsten oxide–polybenzylene hybrids via polymerization of benzyl alcohol and
study of the catalytic activity of the tungsten oxide nanoparticles. Small 2010;6:
11] Dong Y, Su Y, Hu Y, Li H, Xie W. Ag S-CdS p-n nanojunction-enhanced
2
photocatalytic oxidation of alcohols to aldehydes. Small 2020;47:2001529. https://
doi.org/10.1002/smll.202001529.
12] Chen C, Cao Y, Wu X, Cai Y, Liu J, Xu L, Ding K, Yu L. Energy saving and
environment-friendly element-transfer reactions with industrial application
potential. Chin. Chem. Lett. 2020;31:1078–82. https://doi.org/10.1016/
j.cclet.2019.12.019.
9
60–6. https://doi.org/10.1002/smll.200902289.
[
36] Delorme AE, Sans V, Licence P, Walsh DA. Tuning the reactivity of TEMPO during
electrocatalytic alcohol oxidations in room-temperature ionic liquids. ACS Sustain.
Chem. Eng. 2019;7:11691–9. https://doi.org/10.1021/acssuschemeng.9b01823.
37] Amarasekara AS. Acidic ionic liquids. Chem. Rev. 2016;116:6133–83. https://
doi.org/10.1021/acs.chemrev.5b00763.
[
13] Lyu J, Niu L, Shen F, Wei J, Xiang Y, Yu Z, Zhang G, Ding C, Huang Y, Li X. In situ
hydrogen peroxide production for selective oxidation of benzyl alcohol over a Pd@
hierarchical titanium silicalite catalyst. ACS Omega 2020;5:16865–74. https://
doi.org/10.1021/acsomega.0c02065.
[
[
[
14] Murciano LT, Villager T, Chadwick D. Selective oxidation of salicylic alcohol to
38] Gunasekaran N. Aerobic oxidation catalysis with air or molecular oxygen and ionic
liquids. Adv. Synth. Catal. 2015;9:1990–2010. https://doi.org/10.1002/
adsc.201400989.
aldehyde with O
2 2
/H using Au-Pd on titanate nanotubes catalysts. ChemCatChem
2
015;6:925–7. https://doi.org/10.1002/cctc.201403040.
[
15] Ratnam A, Kumari S, Kumar R, Singh UP, Ghosh K. Selective oxidation of benzyl
alcohol catalyzed by ruthenium (III) complexes derived from tridentate mer-ligands
having phenolato donor. J. Organomet. Chem. 2020;905:120986. https://doi.org/
[
[
[
39] Sun W, Sun Q. Bioinspired manganese and iron complexes for enantioselective
oxidation reactions: ligand design, catalytic activity, and beyond. Acc. Chem. Res.
2
019;52:2370–81. https://doi.org/10.1021/acs.accounts.9b00285.
1
0.1016/j.jorganchem.2019.120986.
40] Guomundsson A, Schlipkoter KE, Backvall JE. Iron(II)-catalyzed biomimetic aerobic
[
16] Patil MR, Kapdi AR, Vijay Kumar A. Recyclable supramolecular ruthenium catalyst
for the selective aerobic oxidation of alcohols on water: application to total
synthesis of Brittonin A. ACS Sustain. Chem. Eng. 2018;6:3264–78. https://doi.org/
oxidation of alcohols. Angew. Chem. Int. Ed. 2020;13:5403–6. https://doi.org/
1
0.1002/anie.202000054.
41] Chen C, Zhang X, Cao H, Wang F, Yu L, Xu Q. Iron-enabled utilization of air as the
terminal oxidant leading to aerobic oxidative deoximation by organoselenium
catalysis. Adv. Synth. Catal. 2019;361:603–10. https://doi.org/10.1002/
adsc.201801163.
1
0.1021/acssuschemeng.7b03448.
[
[
[
17] Waldie KM, Flajslik KR, McLoughlin E, Chidsey CED, Waymouth RM.
Electrocatalytic alcohol oxidation with ruthenium transfer hydrogenation catalysts.
J. Am. Chem. Soc. 2017;139:738–48. https://doi.org/10.1021/jacs.6b09705.
[42] Chen X, Mao J, Liu C, Chen C, Cao H, Yu L. An unexpected generation of
18] Wang LY, Li J, Lv Y, Zhang HY, Gao S. Aerobic alcohol oxidation using a PdCl
N-dimethylacetamide catalyst system under mild conditions. J. Organomet. Chem.
011;696:3257–63. https://doi.org/10.1016/j.jorganchem.2011.07.019.
2
/N,
magnetically separable Se/Fe
with molecular oxygen. Chin. Chem. Lett. 2020;31:3205–8. https://doi.org/
0.1016/j.cclet.2020.07.031.
3 4
O for catalytic degradation of polyene contaminants
2
1
19] Karimi B, Khorasani M, Vali H, Vargas C, Luque R. Palladium nanoparticles
supported in the nanospaces of imidazolium-based bifunctional PMOS: the role of
plugs in selectivity changeover in aerobic oxidation of alcohols. ACS Catal. 2015;5:
[
43] Panza N, di Biase A, Rizzato S, Gallo E, Tseberlidis G, Caselli A. Catalytic selective
oxidation of primary and secondary alcohols using nonheme [iron(III)(pyridine-
containing ligand)] complexes. Eur. J. Org Chem. 2020;42:6635–44. https://
doi.org/10.1002/ejoc.202001201.
4
189–200. https://doi.org/10.1021/acscatal.5b00237.
[
[
[
20] Yang JF, Cao K, Gong M, Shan B, Chen R. Atomically decorating of MnOx on
palladium nanoparticles towards selective oxidation of benzyl alcohol with high
yield. J. Catal. 2020;386:60–9. https://doi.org/10.1016/j.jcat.2020.03.029.
21] Zhu J, Kailasam K, Fischer A, Thomas A. Supported cobalt oxide nanoparticles as
catalyst for aerobic oxidation of alcohols in liquid phase. ACS Catal. 2011;1:342–7.
https://doi.org/10.1021/cs100153a.
22] Karthikeyan I, Alamsetti SK, Sekar G. Mechanism of aryl chloride oxidative addition
to chelated palladium(0) complexes. Organometallics 2014;33:1665–73. https://
doi.org/10.1021/om00029a026.
[44] Mozina S, Iskra J. Aerobic oxidation of secondary alcohols with nitric acid and
iron(III) chloride as catalysts in fluorinated alcohol. J. Org. Chem. 2019;84:
1
4579–86. https://doi.org/10.1021/acs.joc.9b02109.
[
45] Tanaka S, Kon Y, Ogawa A, Uesaka Y, Tamura M, Sato K. Mixed picolinate and
quinaldinate iron(III) complexes for the catalytic oxidation of alcohols with
hydrogen peroxide. ChemCatChem 2016;18:2930–8. https://doi.org/10.1002/
cctc.201600362.
4

G. Gopalsamy Selvaraj et al.
Journal of the Indian Chemical Society 98 (2021) 100099
[
46] Yin W, Chu C, Lu Q, Tao J, Liang X, Liu R. Iron chloride/4-acetamido-TEMPO/
sodium nitrite-catalyzed aerobic oxidation of primary alcohols to the aldehydes.
Adv. Synth. Catal. 2010;352:113–8. https://doi.org/10.1002/adsc.200900662.
47] Biswas B, Hunaiti AA, Raisanen MT, Ansaloni S, Leskela M, Repo T, Chen YT,
Tsai HL, Naik AD, Railliet AP, Garcia Y, Ghosh R, Kole N. Efficient and selective
oxidation of primary and secondary alcohols using an iron(III)/phenanthroline
complex: structural studies and catalytic activity. Eur. J. Inorg. 2012;2012:
[51] Karthikeyan P, Muskawar PN, Aswar SA, Kumar SS, Bhagat PR. Development of
highly enantioselective asymmetric aldol reaction catalyzed by 1-glycyl-3-methyl
imidazolium chloride–iron(III) complex. J. Mol. Catal. Chem. 2013;379:333–9.
https://doi.org/10.1016/j.molcata.2013.08.029.
[52] Rani S, Bhat BR. Effective oxidation of alcohols by Iron (III)-Schiff base-
triphenylphosphine complexes. Tetrahedron Lett. 2010;51:6403–5. https://
doi.org/10.1016/j.tetlet.2010.09.109.
[
4
479–85. https://doi.org/10.1002/ejic.201200658.
[53] Hergovich EB, Speier G. Catalytic oxidation of alcohols to carbonyl compounds with
hydrogen peroxide using dinuclear iron complexes. J. Mol. Catal. Chem. 2005;230:
79–83. https://doi.org/10.1016/j.molcata.2004.12.013.
[54] Zhang G, Li S, Lei J, Zhang G, Xie X, Ding C, Liu R. An efficient biomimetic aerobic
oxidation of alcohols catalyzed by iron combined with amino acids. Synlett 2016;
27:956–60. https://doi.org/10.1055/s-0035-1561290.
[55] Jiang X, Zhang J, Ma S. Iron catalysis for room temperature aerobic oxidation of
alcohols to carboxylic acids. J. Am. Chem. Soc. 2016;138:8344–7. https://doi.org/
10.1021/jacs.6b03948.
[56] Shanmugapriya R, Uthayanila S, Ganesh GS, Karthikeyan P. Metal-chloroglynate
ionic liquids: catalytic application for Friedel-crafts reactions. J. Indian Chem. Soc.
2021;98:100081. https://doi.org/10.1016/j.jics.2021.100081.
[
[
[
48] Zhang Z, Khrouz L, Yin G, Andrioletti B. Chalcogen bonding “2S–2N squares” versus
competing interactions: exploring the recognition properties of sulfur. Eur. J. Org
Chem. 2019;2019:323–33. https://doi.org/10.1002/chem.201804261.
49] Steves JE, Preger Y, Martinelli JR, Welch CJ, Root TW, Hawkins JM, Stahl SS.
Process development of CuI/ABNO/NMI-catalyzed aerobic alcohol oxidation. Org.
Process Res. Dev. 2015;19:1548–53. https://doi.org/10.1021/acs.oprd.5b00179.
50] Karthikeyan P, Arunrao AS, Narayan MP, Bhagat PR, Senthil Kumar S. Development
and efficient 1-glycyl-3-methyl imidazolium chloride–copper(II) complex catalyzed
highly enantioselective synthesis of 3, 4-dihydropyrimidin-2(1H)-ones.
J. Organomet. Chem. 2013;723:154–62. https://doi.org/10.1016/
j.jorganchem.2012.06.022.
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