Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and...
Transcript of Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and...
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Supporting Information
Stable and Reusable Nanoscale Fe2O3-catalyzed Aerobic Oxidation Process for Selective Synthesis of Nitriles and Primary Amides
Kathiravan Murugesan, Thirusangumurugan Senthamarai, Manzar Sohail, Muhammad Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh*
Leibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany.
*Corresponding author: E-mail: [email protected]
Table of Contents:S1 Materials and methods
S2 Procedure for the reparation of Fe2O3-N/C (Fe-Phen/C-800) catalyst
S3 General procedure for the preparation of nitriles
S4 General procedure for the preparation of amides
S5 Procedure for the gram scale reactions
S6 Procedure for catalyst recycling
S7 TEM measurements and data of Fe2O3-N/C (Fe-Phen/C-800) catalyst
S8 XPS measurements and data of Fe2O3-N/C (Fe-Phen/C-800) catalyst
S9 EPR and Mössbauer spectral measurements of Fe2O3-N/C (Fe-Phen/C-800) catalyst
S10 NMR Data
S11 References
S12. NMR Spectra
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2017
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S1. Materials and methodsAldehydes, iron acetate, aqueous ammonia (320145 ACS reagent, 28.0-30.0% NH3 basis, Sigma-
Aldrich), 1,10-phenanthroline and other chemicals were obtained from various chemical
companies. Carbon powder, VULCAN® XC72R with Code XVC72R and CAS No. 1333-86-4 was
obtained from Cabot Corporation Prod. The pyrolysis experiments were carried out in Nytech-Qex
oven.
TEM measurements were performed at 200 kV with an aberration-corrected JEM-
ARM200F (JEOL, Corrector: CEOS). The microscope is equipped with a JED-2300 (JEOL)
energy-dispersive x-ray-spectrometer (EDXS) for chemical analysis. The samples were deposited
without any pre-treatment on a holey carbon supported Cu-grid (mesh 300) and transferred to the
microscope. The High-Angle Annular Dark Field (HAADF) and Annular Bright Field (ABF) images
were recorded with a spot size of approximately 0.1nm, a probe current of 120 pA and a
convergence angle of 30-36°. The collection semi-angles for HAADF and ABF were 70-170 mrad
and 11-22 mrad, respectively.
XPS data was obtained with a VG ESCALAB220iXL (ThermoScientific) with monochromatic
Al Kα (1486.6 eV) radiation. The electron binding energies EB were obtained without charge
compensation. For quantitative analysis the peaks were deconvoluted with Gaussian-Lorentzian
curves, the peak areas were divided by a sensitivity factor obtained from the element specific
Scofield factor and the transmission function of the spectrometer.
EPR spectra in X-band were recorded on a Bruker EMX CW-micro spectrometer equipped
with an ER 4119HS-WI high-sensitivity cavity and a variable temperature control unit using the
following parameters: microwave power = 6.64 mW, modulation frequency = 100 kHz, modulation
amplitude = 1 G.
Mössbauer spectra were obtained at 300 K and 77 K by a Mössbauer spectrometer from
Wissel GmbH equipped with a 57Co source. Isomer shifts are given relative to α-Fe at room
temperature. The spectra were analyzed by least-square fits using Lorentzian line shapes.
GC conversions and yields were determined by GC-FID, HP6890 with FID detector,
column HP530 m x 250 mm x 0.25 μm. NMR data were recorded on a Bruker ARX 300 and Bruker
ARX 400 spectrometers.
S2. Procedure for the reparation of Fe2O3-N/C (Fe-Phen/C-800) catalyst (1 g) [2a]
Apropriate amounts of Fe(OAc)2 and 1,10-phenanthroline corresponds to 3 wt% of Fe in 1:3
molar ratio of Fe to phenathroline were stirred in ethanol for 30 minutes at room temperature.
Then, carbon powder (VULCAN® XC72R, Cabot Corperation Prod. Code XVC72R; CAS No.
1333-86-4) was added and the whole reaction mixture was stirred at 60 °C for 12-15 hours.
The reaction mixture was cooled to room temperature and the ethanol was removed in vacuo.
The solid material obtained was dried at 60 °C for 12 hours, after which it was grinded to a fine
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powder. Then, the powdered material was pyrolyzed at 800 °C for 2 hours under an argon
atmosphere and cooled to room temperature.
Elemental analysis of Fe2O3-N/C (pyrolyzed Fe-phen/C at 800 oC) (Wt%): C = 91.1, H = 0.19,
N = 2.69, Fe = 2.95
S3. General procedure for the preparation of nitrilesThe 8 mL oven dried glass vial was charged with magnetic stir bar and 0.5 mmol corresponding
aldehyde and then 2 mL t-amyl alcohol was added. Next, 30 mg Fe2O3-N/C (Fe-Phen/C-800)
catalyst (3 mol% Fe) was added followed the by the addition of 200-300 µL aq. NH3 (28-30% NH3
basis). The glass vial was fitted with septum and screw cap. Then 1 bar O2 containing balloon was
connected to the reaction vial though needle and reaction was allowed to procced for 24 hrs at 40 oC with stirring. After completion of the reaction, the reaction vial was cooled to room
temperature and O2 was discharged. Then, catalyst was filtered off, washed with ethyl acetate.
The solvent from the filtrate containing the reaction product was removed in vacuo and
corresponding nitrile was purified by column chromatography. In case of yields determined by
GC, 100 µL n-hexadecane was added to the reaction vial containing products and diluted with
ethyl acetate. Then, filtered through plug of silica and filtrate contain products was subjected GC
analysis. Conversion and yields were determined by GC-FID (HP6890 with FID detector, column
HP530 m x 250 mm x 0.25 μm) and compared with authentic samples. All products were analyzed
by GC, GC-MS and NMR analysis.
S4. General procedure for the preparation of amides A magnetic stirring bar and the corresponding aldehyde were transferred to 8 mL glass vial and
then the 3 mL H2O was added. Next, 50 mg Fe2O3-N/C (Fe-Phen/C-800) catalyst (5 mol% Fe) was
added followed by the addition of 100 µL aq. NH3 NH3. Then, the vial was fitted with septum, cap
and needle. The reaction vials (8 vials) were placed into a 300 mL autoclave (PARR Instrument
Company) and then autoclave was pressurized with 10 bar of air. The autoclave was placed into
an aluminium block and the temperature of the aluminium block was set to measure 120 oC inside
the autoclave and reactions were allowed to progress under stirred condition for required time at
120 oC. In this set-up the temperature of the aluminium block was set more than 120 oC (130-140 oC) in ordered to attain exactly 120 0C inside the autoclave). After completion of the reactions,
remaining air was discharged and the samples were removed from the autoclave. Then, catalyst
was filtered off, washed with methanol. The solvent from the filtrate containing the reaction product
was removed in vacuo and the corresponding amide was purified by column chromatography. All
products were analyzed by GC-MS and NMR analysis.
S5. Procedure for the gram scale reactionsUnder procedure mentioned in sections S4 with the condition, 2-5 g aldehyde, corresponds to 3
mol% Fe, 200 µL Aq. NH3 for every 0.5 mmol substrate, 40 oC, 10-50 mL t-amyl alcohol, 24-30 h.
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After completion of the reaction, the autoclave was cooled to room temperature and remaining air
was discharged. The catalyst from the reaction mixture was filtered off and washed with ethyl
acetate. The solvent from the filtrate containing reaction products was removed in vacuo. The
corresponding nitrile was purified by column chromatography (silica; n-hexane-ethyl acetate
mixture). All products were analyzed by GC-MS and NMR analysis.
S6. Procedure for catalyst recycling The recycling of the catalyst system was carried out for the synthesis of benzonitrile under the
same procedure given in the section S4 under reaction conditions: 1 mmol benzalydehyde, 60
mg Fe2O3-N/C (Fe-Phen/C-800) (3% Fe), 400 µL aq. NH3, 1 bar O2, 4mL t-amyl alcohol, 40 oC,
24 hrs, yields were determined by GC using 100 µL n-hexadecane standard. In each run,
after the reaction the catalyst was separated by centrifugation, washed thoroughly with ethyl
acetate and dried by vacuum. Then, the dried catalyst was used further, without any
purification or re-activation.
S7. TEM measurements and data of Fe2O3-N/C (Fe-Phen/C-800) catalyst
TEM investigation of Fe-Phen/C-800 material (Fig. S1) was characterized by the formationFe2O3
particles of different size. Most of the oxide particles have a size between 20 and 80 nm, but occur
always together with smaller ones of 2-5 nm size. Interestingly, these particles, including the small
ones, are surrounded by a shell of a few graphene layers (best visible in the ABF image; Fig. S;
left). The oxidic nature of the particles has been confirmed by Mössbauer, XPS and EPR results
discussed below.
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Fig. S1. TEM images of (A): Fe2O3-N/C (Fe-Phen/C-800)-catalyst: Right=HAADF image showing
the distribution Fe2O3-particles; Middle= image showing Fe2O3-particle surrounded by nitrogen
doped graphene layers; Right: EDXS map : iron = green, oxygen = red, carbon = blue.
(B): Fe(OAc)2/C-800 material, in which there is o formation of nitrogen doped graphene layers.
Fig. S2. EDX analysis of the Fe2O3 particles
Fe C O
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S8. XPS mesurments and data of of Fe2O3-N/C (Fe-Phen/C-800) catalyst XPS studies of Fe2O3-N/C (Fe-Phen/C-800) catalyst have been revealed that (Fig. S3)
there are three N1s peaks occur at 398.3 eV, 399.3 eV and 401.0 eV. The first two peaks are
assigned to pyridinic nitrogen and Fe-N centers, respectively 1. A similar shift and even a splitting
of the N1s peak was observed for 2H-tetraphenylporphyrin monolayers in contact with deposited
Fe atoms on top. It was assigned to a so-called distorted FeN4-center, 2 in which the Fe-N
distances are slightly different, thus, giving rise to the peak splitting. It is probable that similar FeNx-
centers are formed with progressing pyrolysis on the surface of the emerging iron oxide particles.
The fact that no splitting of the peak at 399.3 eV is observed may be due to a distribution of Fe-N
distances which just contributes to the line width. The third N1s peak observed can be assigned to
nitrogen in a graphite-like structure. 1 This suggests that N is incorporated into the support lattice.
The XPS for Fe2P electrons, two peaks corresponding to Fe species in the near-surface
region were observed. The first one (major) appeared at 712.4 eV and the second one (minor) at
709.9 eV. The first peak is due to the presence of Fe+3 species (more likely Fe2O3) while the
second one is assigned to Fe+2 species. Fe+2 species are in minor proportion compared to Fe+3.
Literature survey3 reveals that the B.E. value of Fe 2p3/2 higher than 710.2 eV can be assigned to
Fe3+ and the peak at 709.9 eV can be attributed to the presence of Fe+2 species.4 Based on these
results, in Fe-Phen/C-800 catalyst, both Fe+3 (major) and Fe+2 (minor) species are presented on
the surface of the material. However, the bulk composition is somewhat different from the surface
composition. In the bulk, we could see the presence of mainly the Fe+3 species (in the form of
Fe2O3). The presence of Fe2O3 as particles has been confirmed by EPR analysis Mössbauer
spectral analysis as follows.
Fig. S3 A. XP spectra of the N1s electrons for the Fe2O3-N/C (Fe-Phen/C-800) catalyst
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S7
Fig. S3B. XP spectra of the Fe2P electrons for the Fe2O3-N/C (Fe-Phen/C-800) catalyst.
S9. EPR and Mössbauer spectral mesurments of Fe2O3-N/C (Fe-Phen/C-800) catalyst
The material Fe2O3-N/C (Fe-Phen/C-800) shows broad anisotropic signals at low temperature
which are characteristic for the presence of ferromagnetic domains/particles of different size and/or
shape (Fig. S4). The magnetic moments of such particles tend to align to the static magnetic field
of the spectrometer at low temperature. However, with rising temperature thermal fluctuations of
the magnetic moments became dominant which lift this alignment and gave rise to isotropic signals
above the so-called blocking temperature Tb. This effect is called super-paramagnetic resonance.5
The smaller the particle dimension, the lower is TB and is may be above 380 K since the anisotropy
of the signal is still persistent (Fig. S4).
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Fig. S4. EPR spectra of Fe2O3-N/C (Fe-Phen/C-800) catalyst measured as a function of
temperature By EPR spectroscopy alone it is not possible to identify the phase of the
superparamagnetic particles. Given the thermal pre-treatment in argon atmosphere rather the
formation of zero-valent iron than of ferric oxide particles was expected. Since EPR can hardly
distinguish between ferromagnetic and/or superparamagnetic particles of those phases,
Mössbauer spectra have been recorded in addition (Fig. S5). In the Mössbauer spectra, C1 turns
into a magnetically split sextet with hyperfine field of Bhf = 50.5 T and 50.3 T at 300 K, which
comprises about 50 % and 71 % at 77 K, respectively, of all Fe species. The hyperfine field is
comparable to that of -Fe2O3.6 Besides, sample contains a minor amount of high-spin Fe(II)
reflected by component C3. In all samples, the presence of metallic iron phases or iron carbide can
be excluded. Metallic iron phases would exhibit a magnetic hyperfine field of 33 T at room
temperature and carbidic iron phases would have even less hyperfine fields. Moreover, the
observed isomer shifts do not agree with the expected values for such phases. Based on EPR and
Mössbauer results it can be concluded that thermal pre-treatment and subsequent exposure of the
catalyst to ambient atmosphere at room temperature leads to the formation of super-paramagnetic
Fe2O3 particles, the relative percentage (with respect to the total Fe content) and the size of which
increases with rising pre-treatment temperature. This agrees properly with the TEM results. Given
that thermal pre-treatment has been performed in the absence of oxygen, it is possible that metallic
Fe was formed initially but oxidized quickly upon contact with ambient atmosphere. More likely,
oxygen from the acetate ligands is directly incorporated.
Table S1. Isomer shifts , quadrupole splitting EQ, hyperfine field Bhf and relative intensity Irel as
obtained by the analysis of the Mössbauer spectra plotted in Fig. S5
Catalyst T / K Component / mm s-1 EQ / mm s-1 Irel / % Bhf / T
Fe2O3-N/C 300 C1 0.35 0 71 50.3
C2 0.38 1.00 29
77 C1 0.4 0 56 52.4
C2 0.48 1.00 44
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S9
Fig. S5. Mössbauer spectra of Fe2O3-N/C catalyst measured at 300 and 77 K. The solid lines
have been calculated assuming doublets and sextets with lorentzian line shape
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0 200 400 600 800 1000 12000
20
40
60
80
100 (A)
Aq. NH4 (micro L)
Yiel
d of
ben
zoni
trile
(%)
0 5 10 15 20 25 30 350102030405060708090100 (B)
Time (h)
Yiel
d of
ben
zoni
trile
(%)
0 5 10 15 20 25 30 35 40 450
20
40
60
80
100 (C)
Catalyst (mg)
Yiel
d of
bne
zoni
trile
(%)
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S11
0 1 2 3 40
20
40
60
80
100 (D)
Benzaldehyde (mmol)
Yiel
d of
ben
zoni
trile
0 1 2 3 4 5 60
20
40
60
80
100
(E)
O2 (bar)
Yiel
d of
ben
zoni
trile
(%)
Fig. S6. Kinetics plots of yield of benzonitriles Vs. Aq. NH3 (A), time (B), catalyst (C), concentration
of benzaldehyde (D) and pressure oxygen (E). Reaction conditions: (A) = 0.5 mmol benzaldehyde, 50-1000 µL aq. NH3 (28-30% NH3 basis), 30
mg catalyst (3 mol% Fe), 1 bar O2 (balloon), 2 mL t-amyl alcohol, 40 °C, 24 h. (B)= 0.5 mmol
benzaldehyde, 200 µL aq. NH3 (28-30% NH3 basis), 30 mg catalyst (3 mol% Fe), 1 bar O2
(balloon), 2 mL t-amyl alcohol, 40 °C, 5-30 h. (C)= 0.5 mmol benzaldehyde, 200 µL aq. NH3 (28-
30% NH3 basis), 5-40 mg catalyst (3 mol% Fe), 1 bar O2 (balloon), 2 mL t-amyl alcohol, 40 °C, 24
h. (D)= 0.5-3.0 mmol benzaldehyde, 200 µL aq. NH3 (28-30% NH3 basis), 30 mg catalyst (3 mol%
Fe), 1 bar O2 (balloon), 2 mL t-amyl alcohol, 40 °C, 24 h. (E)= 0.5 mmol benzaldehyde, 200 µL
aq. NH3 (28-30% NH3 basis), 30 mg catalyst (3 mol% Fe), 1-5 bar O2 (balloon), 2 mL t-amyl
alcohol, 40 °C, 24 h.
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S12
S10. NMR dataKM11-11
SCN
1H NMR (300 MHz, Chloroform-d) δ 7.78 – 7.62 (m, 2H), 7.53 – 7.26 (m, 2H), 2.52 (s, 3H). 13C NMR (75 MHz, Chloroform-d) δ 145.22 , 140.78 , 137.55 , 127.92 , 125.35 , 123.52 , 122.66 , 114.57 , 105.59 , 13.75 . Yellow solid.
KM11-17
CNO
O
1H NMR (300 MHz, Chloroform-d) δ 7.17 – 6.96 (m, 2H), 6.93 – 6.70 (m, 1H), 4.33 – 4.11 (m, 4H). 13C NMR (75 MHz, Chloroform-d) δ 147.75 , 143.80 , 125.87 , 121.21 , 118.91 , 118.25 , 104.38 , 64.59 , 64.12 . Off white solid
KM11-21
CN
1H NMR (300 MHz, Chloroform-d) δ 7.38 – 6.96 (m, 5H), 3.19 – 2.89 (m, 1H), 2.61 – 2.31 (m, 2H), 1.37 (d, J = 7.0 Hz, 3H). 13C NMR (75 MHz, Chloroform-d) δ 143.16 , 128.88 , 127.35 , 126.57 , 118.63 , 36.55 , 26.36 , 20.70 . Yellow gum.
KM11-27
N
CN
1H NMR (300 MHz, Chloroform-d) δ 8.62 (d, J = 3.0 Hz, 1H), 8.59 (dd, J = 4.9, 1.6 Hz, 1H), 7.74-7.72 (m, 1H), 7.39 – 7.26 (m, 2H), 5.92 (d, J = 16.7 Hz, 1H). 13C NMR (75 MHz, Chloroform-d) δ 151.89 , 148.99 , 147.02 , 133.53 , 129.30 , 123.89 , 117.35 , 98.82 . Pale yellow solid.
KM11-28
CN
Br
1H NMR (300 MHz, Chloroform-d) δ (d, J = 9 Hz, 2H), 7.29 – 7.19 (m, 3H), 5.80 (d, J = 16.6 Hz, 1H). 13C NMR (75 MHz, Chloroform-d) δ 149.20 , 132.49 , 132.37 , 128.73 , 125.62 , 117.84 , 97.10 . Yellow solid.
KM11-32
N
CN
Cl
1H NMR (300 MHz, Chloroform-d) δ 8.37 (s, 1H), 7.62 (m, 2H), 7.47 (dd, J = 8.2, 7.0 Hz, 1H), 2.64 (s, 3H). 13C NMR (75 MHz, Chloroform-d) δ 147.29 , 147.01 , 144.95 , 137.31 , 134.02 , 128.46 , 125.92 , 125.14 , 115.31 , 107.40 , 17.63 . Yellow solid.
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S13
KM11-54
NN Cl
CNF
FF
1H NMR (300 MHz, Chloroform-d) δ 3.90 (s, 3H). 13C NMR (75 MHz, Chloroform-d) δ 143.20 (q, J = 212.0 Hz), 135.50 , 119.07 (q, J = 270.7 Hz), 108.90 , 91.42 , 37.87 . Colorless oil.
KM11-57
O
CNOF
F
1H NMR (300 MHz, Chloroform-d) δ 7.28 – 7.13 (m, 3H), 7.04 – 6.89 (m, 3H), 5.18 (s, 2H), 3.76 (s, 3H). 13C NMR (75 MHz, Chloroform-d) δ 162.07 (d, J = 252.0 Hz), 152.03 , 150.00 , 131.16 (d, J = 9.9 Hz), 126.24 , 125.67 (d, J = 3.5 Hz), 119.17 , 114.82 , 114.43 (d, J = 22.5 Hz), 113.91 , 104.76 , 62.33 (d, J = 4.1 Hz), 56.27 . White solid.
KM11-230
CN
Cl
Cl
1H NMR (300 MHz, Chloroform-d) δ 7.67 – 7.03 (m, 3H). 13C NMR (75 MHz, Chloroform-d) δ 138.43 , 134.00 , 128.21 , 114.31 , 113.35 . White solid.
KM11-58
O
O
CN
NO2
1H NMR (300 MHz, DMSO-d6) δ 7.94 (s, 1H), 7.73 (s, 1H), 6.39 (s, 2H). 13C NMR (75 MHz, DMSO-d6) δ 152.93 , 152.19 , 145.13 , 115.89 , 113.50 , 106.59 , 105.62 , 102.06 . Yellow solid.
KM11-3
CN
NH2Br
Br
1H NMR (300 MHz, Chloroform-d) δ 7.65 (d, J = 2.2 Hz, 1H), 7.40 (d, J = 2.2 Hz, 1H), 4.84 (br s, 2H). 13C NMR (75 MHz, Chloroform-d) δ 146.21 , 139.38 , 133.60 , 115.61 , 109.74 , 108.20 , 97.90 . White solid.
KM11-4
CN
1H NMR (300 MHz, Chloroform-d) δ 7.55 – 7.00 (m, 6H), 5.78 (d, J = 16.7 Hz, 1H). 13C NMR (75 MHz, Chloroform-d) δ 150.59 , 133.52 , 131.25 , 129.14 , 127.40 , 118.22 , 96.35 . Colorless oil.
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S14
KM11-12
CN
FF
F
1H NMR (300 MHz, Chloroform-d) δ 7.45 – 7.01 (m, 2H). 13C NMR (75 MHz, DMSO-d6) δ 151.46 (ddd, J = 236.6, 9.8, 3.5 Hz), 143.44 (dt, J = 243.6, 13.3 Hz), 117.34 (dt, J = 23.1, 8.4 Hz), 115.93 (t, J = 2.8 Hz), 108.0 (td, J = 14.0, 4.9 Hz). Colorless gum.
KM11-34
CN
1H NMR (300 MHz, Chloroform-d) δ 7.46 – 6.89 (m, 5H), 2.85 (t, J = 7.4 Hz, 2H), 2.50 (t, J = 6.0 Hz, 2H). 13C NMR (75 MHz, Chloroform-d) δ 138.12 , 128.89 , 128.31 , 127.25 , 119.23 , 31.57 , 19.36 . Colorless oil.
KM11-53
CNF
FF
FFF
1H NMR (300 MHz, Chloroform-d) δ 8.95 – 8.10 (m, 3H). 13C NMR (75 MHz, Chloroform-d) δ 133.23 (q, J = 34.8 Hz), 132.22 (q, J = 3.8 Hz), 125.75 (q, J = 253.4 Hz) 126.48 (hept, J = 3.3 Hz), 115.89 , 114.87 . Colorless oil.
KM11-79
CN
1H NMR (300 MHz, Chloroform-d) δ 7.44 – 7.15 (m, 10H), 5.05 (s, 1H). 13C NMR (75 MHz, Chloroform-d) δ 135.92 , 129.22 , 128.28 , 127.75 , 119.72 , 42.62 . Pale Yellow solid.
KM11-95
CN
1H NMR (300 MHz, Chloroform-d) δ 7.64 – 7.55 (m, 4H), 7.52 – 7.46 (m, 2H), 7.42 – 7.29 (m, 3H). 13C NMR (75 MHz, Chloroform-d) δ 145.66 , 139.16 , 132.61 , 129.14 , 128.69 , 127.74 , 127.24 , 118.98 , 110.91 . White solid.
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S15
KM11-70
CN
1H NMR (300 MHz, Chloroform-d) δ 7.65 – 6.95 (m, 10H), 5.62 (s, 1H). 13C NMR (75 MHz, Chloroform-d) δ 163.15 , 138.94 , 137.10 , 130.50 , 130.09 , 129.61 , 128.72 , 128.61 , 128.53 , 117.98 , 94.95 .
KM11-74 (cis trans isomer mixture)
N
1H NMR (300 MHz, Chloroform-d) δ 5.19 – 4.75 (m, 2H), 2.41 – 2.26 (m, 1H), 2.20 – 2.04 (m, 3H), 1.91 (m, 3H), 1.62 (dt, J = 2.5, 1.3 Hz, 3H), 1.58 – 1.50 (m, 3H). 13C NMR (75 MHz, Chloroform-d) δ 165.13 , 165.02 , 133.32 , 133.20 , 122.21 , 122.16 , 117.28 , 116.98 , 95.80 , 95.22 , 38.57 , 36.28 , 26.13 , 25.65 , 25.62 , 25.60 , 22.90 , 21.03 , 17.72 , 17.66 .KM11-76
O
O
CN
Br
1H NMR (300 MHz, Chloroform-d) δ 7.00 (s, 1H), 6.94 (s, 1H), 6.04 (s, 2H). 13C NMR (75 MHz, Chloroform-d) δ 152.28 , 147.49 , 118.90 , 117.36 , 113.36 , 112.50 , 107.80 , 103.17 . White solid
KM11-77
CN
1H NMR (300 MHz, Chloroform-d) δ 7.53 – 7.37 (m, 6H), 7.33 – 7.16 (m, 3H), 7.09 (d, J = 16.4 Hz, 1H), 6.95 (d, J = 16.4 Hz, 1H). 13C NMR (75 MHz, Chloroform-d) δ 141.83 , 136.30 , 132.52, 132.40 , 128.89 , 128.68 , 126.96 , 126.89 , 126.72 , 119.10 , 110.54 . White solid.
KM11-142
CN
1H NMR (300 MHz, Chloroform-d) δ 7.36 – 7.19 (m, 5H), 7.11 – 7.10 (m, 1H), 2.04 (s, 3H). 13C NMR (75 MHz, Chloroform-d) δ 144.43 , 133.94 , 129.35 , 129.32 , 128.71 , 121.13 , 109.49 , 16.82 . Pale Yellow gum.
KM11-144
OCN
1H NMR (300 MHz, Chloroform-d) δ 7.48-7.72 (m, 1H), 7.03 (d, J = 20.00 Hz, 1H), 6.41-6.55 (m, 2H), 5.68 (d, J = 20.00 Hz, 1H). 13C NMR (75 MHz, Chloroform-d) δ 149.79 , 145.47 , 136.15 , 118.28 , 115.47 , 112.64 , 93.34 . Brown gum.
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S16
KM11-146
CN
1H NMR (300 MHz, Chloroform-d) δ 6.58 (m,1H), 4.74 – 4.70 (m, 1H), 4.64 (m, 1H), 2.32 – 2.19 (m, 3H), 2.14 – 2.03 (m, 2H), 1.86 – 1.77 (m, 1H), 1.69 – 1.65 (m, 3H), 1.52 – 1.39 (m, 1H). 13C NMR (75 MHz, Chloroform-d) δ 147.72 , 144.62 , 119.53 , 112.06 , 109.84 , 39.20 , 30.96 , 26.93 , 26.28 , 20.63 . Yellow oil.
KM11-148
NH2
O
1H NMR (300 MHz, DMSO-d6) δ 7.91 (br s, 1H), 7.8 (d, J = 6.00 Hz, 2H), 7.28 (br s, 1H), 7.2 (d, J = 9.00 Hz, 2H), 2.34 (s, 3H). 13C NMR (75 MHz, DMSO-d6) δ 168.32 , 141.50 , 131.96 , 129.18 , 127.98 , 21.39 . White solid.
KM11-162
S
O
NH2
1H NMR (300 MHz, DMSO-d6) δ 8.14 (dd, J = 3.0, 1.3 Hz, 1H), 7.78 (br s, 1H), 7.56 (dd, J = 5.0, 2.9 Hz, 1H), 7.49 (dd, J = 5.0, 1.3 Hz, 1H), 7.23 (br s, 1H). 13C NMR (75 MHz, DMSO-d6) δ 164.16 , 138.47 , 129.45 , 127.62 , 126.99 . Offwhite solid.KM11-190
NH2
OO
O
1H NMR (300 MHz, DMSO-d6) δ 7.81 (br s, 1H), 7.48 (dd, J = 8.1, 1.8 Hz, 1H), 7.41 (dd, J = 1.8, 0.4 Hz, 1H), 7.23 (br s, 1H), 6.97 (d, J = 9.0 Hz, 1H), 6.09 (s, 2H). 13C NMR (75 MHz, DMSO-d6) δ 167.45 , 150.14 , 147.70 , 128.77 , 122.96 , 108.19 , 108.02 , 102.05 . Yellow solid.
KM11-196
NH2
O
Br
1H NMR (300 MHz, DMSO-d6) δ 7.87 (br s, 1H), 7.69 – 7.62 (m, 1H), 7.58 (br s, 1H), 7.46 – 7.39 (m, 2H), 7.35 – 7.31 (m, 1H). 13C NMR (75 MHz, DMSO-d6) δ 169.54 , 139.81 , 133.18 , 131.11 , 129.03 , 127.95 , 119.09 . White solid
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S17
KM11-197
O
Cl
NH2
1H NMR (300 MHz, DMSO-d6) δ 7.89 (br s, 1H), 7.60 (br s, 1H), 7.54 – 7.34 (m, 4H). 13C NMR (75 MHz, DMSO-d6) δ 168.67 , 137.60 , 131.02 , 130.14 , 130.07 , 129.14 , 127.47 . White solid
KM11-198
NH2
O
F
F F
F
FF
1H NMR (300 MHz, DMSO-d6) δ 8.17 (br s, 1H), 8.02 (dd, J = 1.8, 0.7 Hz, 2H), 7.91 – 7.80 (m, 1H), 7.83 (br s, 1H). 13C NMR (75 MHz, DMSO-d6) δ 167.98 , 138.32 (q, J = 2.1 Hz), 132.90 (q, J = 32.6 Hz), 129.90 (q, J = 33.4 Hz), 128.19 (q, J = 4.9 Hz), 126.94 (q, J = 3.7 Hz), 125.67 (q, J = 3.8 Hz), 123.39 (q, J = 253.4 Hz), 123.21 (q, J = 254.8 Hz)).Yellow soild
KM11-199
NH2
O
F
1H NMR (300 MHz, DMSO-d6) δ 8.04 – 7.92 (m, 3H), 7.41 (br s, 1H), 7.32 – 7.23 (m, 2H). 13C NMR (75 MHz, DMSO-d6) δ 167.35 , 164.39 (d, J = 248.4 Hz), 131.20 (d, J = 2.9 Hz), 130.57 (d, J = 9.0 Hz), 115.52 (d, J = 21.7 Hz). White solid.
KM11-202
SO
NH2
1H NMR (300 MHz, DMSO-d6) δ 7.99 (br s, 1H), 7.80 – 7.68 (m, 2H), 7.40 (br s, 1H), 7.13 (m, 1H). 13C NMR (75 MHz, DMSO-d6) δ 163.44 , 140.73 , 131.41 , 129.18 , 128.34 . White solid.
KM11-205
SO
NH2
1H NMR (300 MHz, DMSO-d6) δ 7.54 (d, J = 8.0, Hz, 1H), 7.34 (br s, 2H), 6.94 (d, J = 8.0, Hz, 1H), 2.43 (s, 3H). 13C NMR (75 MHz, DMSO-d6) δ 164.63 , 140.41 , 132.34 , 132.04 , 127.72 , 15.79 . White solid.
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S18
KM11-214
NNH2
O
1H NMR (300 MHz, DMSO-d6) δ 8.61 (dt, J = 3.2, 1.9 Hz, 1H), 8.17 (br s, 1H), 8.11 – 8.03 (m, 1H), 8.01 – 7.90 (m, 1H), 7.71 (br s, 1H), 7.56 – 7.53 (m, 1H). 13C NMR (75 MHz, DMSO-d6) δ 166.58 , 150.73 , 148.86 , 138.04 , 126.86 , 122.37 . White solid.
KM11-211
NH2
O
NO2
1H NMR (300 MHz, DMSO-d6) δ 8.17 (br s, 1H), 8.01 (ddd, J = 8.0, 1.3, 0.5 Hz, 1H), 7.82 – 7.73 (m, 1H), 7.73 – 7.60 (m, 3H). 13C NMR (75 MHz, DMSO-d6) δ 167.69 , 147.69 , 133.78 , 133.06 , 131.06 , 129.30 , 124.39 . White solid.
KM11-211
NH2
O
O
FFF
1H NMR (300 MHz, DMSO-d6) δ 13.22 (br s, 1H), 8.07 (d, J = 9.0, Hz, 2H), 7.48 (d, J = 6.0, Hz, 2H), 3.33 (br s, 1H). 13C NMR (75 MHz, DMSO-d6) δ 166.62 , 151.90 , 132.15 , 130.33 , 125.29 (q, J = 238.7 Hz), 121.15 . White solid.
S11. References1. F. Jaouen, et al., ACS Appl. Mater. Interfaces, 2009, 1, 1623-1639.
2. F. Buchner, K. Flechtner, Y. Bai, E. Zillner, I. Kellner, H. Steinrück, H. Marbach, J. M.
Gottfried, J. Phys. Chem. C, 2008, 112, 15458-15465.
3. (a) M. Descostes, F. Mercier, N. Thromat, C. Beaucaire, M. Gautier-Soyer, Appl.Surf. Sci.
2000, 165, 288-302; (b) J.F. Moulder, W.F. Stickle, P.E. Sobol, K.D. Bomben, Handbook
of X-ray Photoelectron Spectroscopy, Perkin-Elmer Corp., Eden Praire, MN, 1992.
4. (a) M. Stöcker, Microporous Mater. 1996, 6, 235–257; (b) P. Grosvenor, B.A. Kobe, M.C.
Biesinger, N.S. McIntyre, Surf. Interface Anal. 2004, 36, 1564–1574.
5. R. Berger, J-C. Bissey, J. Kliava, H. Daubric, C. Estournès, J. Magn. Mater. 2001, 234,
535.
6. H. Huang, R. Christmann, R. Ulber, V. Schünemann, Hyperfine Interactions, 2012 205,
121–124
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S19
S12. NMR spectra
-4-3-2-10123456789101112131415f1 (ppm)
170524.316.1.fidKathir KM11-11Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 16
3.00
1.99
1.97
![Page 20: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/20.jpg)
S20
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170524.316.2.fidKathir KM11-11Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 16 13
.75
105.
59
114.
57
122.
6612
3.52
125.
3512
7.92
137.
5514
0.78
145.
22
-3-2-1012345678910111213141516f1 (ppm)
170524.317.1.fidKathir KM11-17Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 17
4.37
1.00
1.88
6.81
6.82
6.84
6.84
6.84
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S21
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170524.317.2.fidKathir KM11-17Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 17 64
.12
64.5
9
104.
38
118.
2511
8.91
121.
2112
5.87
143.
8014
7.75
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S22
-4-3-2-10123456789101112131415f1 (ppm)
170526.303.1.fidKathir KM11-21Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 3
3.00
2.16
1.05
5.54
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.303.2.fidKathir KM11-21Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 3 20
.70
26.3
6
36.5
5
118.
63
126.
5712
7.35
128.
88
143.
16
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S23
2.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.513.013.514.014.515.015.516.0f1 (ppm)
170526.305.1.fidKathir KM11-27Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 5
1.00
2.01
1.27
0.83
0.96
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.305.2.fidKathir KM11-27Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 5 98
.82
117.
3512
3.89
129.
3013
3.53
147.
0214
8.99
151.
89
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S24
2.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.513.013.514.014.515.015.516.0f1 (ppm)
170526.306.1.fidKathir KM11-28Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 6
1.00
3.27
1.86
5060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.306.2.fidKathir KM11-28Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 6 97
.10
117.
84
125.
6212
8.73
132.
3713
2.49
149.
20
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S25
-4-3-2-1012345678910111213141516f1 (ppm)
170526.307.1.fidKathir KM11-32Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 7
3.00
0.89
1.81
0.90
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.307.2.fidKathir KM11-32Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 7 17
.63
107.
40
115.
31
125.
1412
5.92
128.
4613
4.02
137.
31
144.
9514
7.01
147.
29
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S26
-3-2-1012345678910111213141516f1 (ppm)
170526.310.1.fidKathir KM11-54Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 10
3.00
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.310.2.fidKathir KM11-54Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 10 37
.87
91.4
2
108.
9011
3.69
117.
2712
0.86
124.
44
135.
5014
2.40
142.
9314
3.46
143.
99
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S27
-4-3-2-1012345678910111213141516f1 (ppm)
170526.311.1.fidKathir KM11-57Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 11
3.00
1.98
2.82
2.84
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.311.2.fidKathir KM11-57Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 11 56
.27
62.3
062
.35
104.
7611
3.91
114.
2811
4.58
114.
8211
9.17
121.
3712
1.60
125.
6412
5.69
126.
2413
1.09
131.
22
150.
0015
2.03
160.
4016
3.73
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S28
-3-2-1012345678910111213141516f1 (ppm)
170628.f347.10.fidKathir/ KM11-230PROTON CDCl3 {C:\Bruker\TopSpin3.5pl6} 1706 47
3.00
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
170628.f347.11.fidKathir/ KM11-230C13CPD CDCl3 {C:\Bruker\TopSpin3.5pl6} 1706 47 11
3.35
114.
31
128.
21
134.
00
138.
43
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S29
-3-2-1012345678910111213141516f1 (ppm)
170526.324.1.fidKathir KM11-58Au1H DMSO {C:\Bruker\TopSpin3.5pl6} 1705 24
2.00
0.86
0.83
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.324.2.fidKathir KM11-58Au13C DMSO {C:\Bruker\TopSpin3.5pl6} 1705 24 10
2.06
105.
6210
6.59
113.
5011
5.89
145.
13
152.
1915
2.93
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S30
-4-3-2-1012345678910111213141516f1 (ppm)
170526.325.1.fidKathir KM11-3Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 25
1.86
1.00
1.00
4.84
7.40
7.41
7.64
7.65
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.325.2.fidKathir KM11-3Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 25 97
.90
108.
2010
9.74
115.
61
133.
60
139.
38
146.
21
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S31
-4-3-2-10123456789101112131415f1 (ppm)
170526.326.1.fidKathir KM11-4Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 26
1.00
6.10
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.326.2.fidKathir KM11-4Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 26 96
.35
118.
22
127.
4012
9.14
131.
2513
3.52
150.
59
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S32
-4-3-2-1012345678910111213141516f1 (ppm)
170526.327.1.fidKathir KM11-12Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 27
2.00
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.327.2.fidKathir KM11-12Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 27 10
7.83
107.
9110
7.96
108.
0410
8.10
108.
1711
5.90
117.
1811
7.29
117.
3911
7.51
141.
5114
1.71
141.
9014
4.99
145.
1914
5.38
149.
6814
9.73
149.
8214
9.87
153.
0615
3.11
153.
2015
3.25
![Page 33: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/33.jpg)
S33
-4-3-2-10123456789101112131415f1 (ppm)
170526.328.1.fidKathir KM11-34Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 28
2.00
2.03
4.82
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.328.2.fidKathir KM11-34Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 28 19
.36
31.5
7
119.
23
127.
2512
8.31
128.
89
138.
12
![Page 34: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/34.jpg)
S34
-4-3-2-1012345678910111213141516f1 (ppm)
170526.329.1.fidKathir KM11-53Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 29
3.00
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.329.2.fidKathir KM11-53Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 29 11
4.87
115.
8911
6.70
120.
3212
3.94
126.
3412
6.38
126.
4312
6.48
126.
5312
6.57
126.
6212
7.56
132.
1513
2.20
132.
2513
2.30
132.
5413
3.00
133.
4613
3.93
![Page 35: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/35.jpg)
S35
-4-3-2-10123456789101112131415f1 (ppm)
170526.330.1.fidKathir KM11-79Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 30
1.00
10.1
0
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.330.2.fidKathir KM11-79Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 30 42
.62
119.
72
127.
7512
8.28
129.
2213
5.92
![Page 36: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/36.jpg)
S36
-4-3-2-10123456789101112131415f1 (ppm)
170526.331.1.fidKathir KM11-95Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 31
3.00
1.98
4.00
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170526.331.2.fidKathir KM11-95Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 31 11
0.91
118.
98
127.
2412
7.74
128.
6912
9.14
132.
6113
9.16
145.
66
![Page 37: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/37.jpg)
S37
-4-3-2-10123456789101112131415f1 (ppm)
170529.326.1.fidKathir KM11-70Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 26
1.00
10.2
8
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170529.326.2.fidKathir KM11-70Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 26 94
.95
117.
9812
8.53
128.
6112
8.72
129.
6113
0.09
130.
5013
7.10
138.
94
163.
15
![Page 38: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/38.jpg)
S38
-3-2-1012345678910111213141516f1 (ppm)
170529.328.1.fidKathir KM11-74Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 28
3.00
3.19
3.11
3.19
1.03
1.93
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170529.328.2.fidKathir KM11-74Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 28 17
.66
17.7
221
.03
22.9
025
.60
25.6
225
.65
26.1
336
.28
38.5
7
95.2
295
.80
116.
9811
7.28
122.
1612
2.21
133.
2013
3.32
165.
0216
5.13
![Page 39: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/39.jpg)
S39
-3-2-1012345678910111213141516f1 (ppm)
170529.329.1.fidKathir KM11-76Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 29
2.00
0.82
0.84
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170529.329.2.fidKathir KM11-76Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 29 10
3.17
107.
8011
2.50
113.
3611
7.36
118.
90
147.
49
152.
28
![Page 40: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/40.jpg)
S40
-4-3-2-10123456789101112131415f1 (ppm)
170529.330.1.fidKathir KM11-77Au1H CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 30
1.07
1.09
3.04
6.00
-100102030405060708090100110120130140150160170180190200210220230240250260270f1 (ppm)
170529.330.2.fidKathir KM11-77Au13C CDCl3 {C:\Bruker\TopSpin3.5pl6} 1705 30 11
0.54
119.
1012
6.72
126.
8912
6.96
128.
6812
8.89
132.
4013
2.52
136.
3014
1.83
![Page 41: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/41.jpg)
S41
-3-2-1012345678910111213141516f1 (ppm)
170613.f340.10.fidKathir KM11-142PROTON CDCl3 {C:\Bruker\TopSpin3.5pl6} 1706 40
3.00
0.90
4.84
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
170613.f340.11.fidKathir KM11-142C13CPD CDCl3 {C:\Bruker\TopSpin3.5pl6} 1706 40 16
.82
109.
68
121.
29
128.
7112
9.32
129.
3513
4.12
144.
43
![Page 42: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/42.jpg)
S42
-3-2-1012345678910111213141516f1 (ppm)
170613.f342.10.fidKathir KM11-144PROTON CDCl3 {C:\Bruker\TopSpin3.5pl6} 1706 42
1.00
2.14
0.78
0.94
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
170613.f342.11.fidKathir KM11-144C13CPD CDCl3 {C:\Bruker\TopSpin3.5pl6} 1706 42 93
.34
112.
6411
5.47
118.
28
136.
15
145.
47
149.
79
![Page 43: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/43.jpg)
S43
-3-2-1012345678910111213141516f1 (ppm)
170613.f344.10.fidKathir KM11-146PROTON CDCl3 {C:\Bruker\TopSpin3.5pl6} 1706 44
1.49
3.00
1.54
2.02
3.06
1.22
1.08
0.90
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
170613.f344.11.fidKathir KM11-146C13CPD CDCl3 {C:\Bruker\TopSpin3.5pl6} 1706 44 20
.63
26.2
826
.93
30.9
6
39.2
0
109.
8411
2.06
119.
53
144.
6214
7.72
![Page 44: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/44.jpg)
S44
-3-2-1012345678910111213141516f1 (ppm)
170619.f337.10.fidKathir KM11-148PROTON DMSO {C:\Bruker\TopSpin3.5pl6} 1706 37
3.00
2.13
0.53
2.03
0.85
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
21.3
9
127.
9812
9.18
131.
96
141.
50
168.
32
![Page 45: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/45.jpg)
S45
-3-2-1012345678910111213141516f1 (ppm)
170619.f338.10.fidKathir KM11-162PROTON DMSO {C:\Bruker\TopSpin3.5pl6} 1706 38
0.92
0.94
0.92
0.97
1.00
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
126.
9912
7.62
129.
45
138.
47
164.
16
![Page 46: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/46.jpg)
S46
-3-2-1012345678910111213141516f1 (ppm)
170619.f339.10.fidKathir KM11-190PROTON DMSO {C:\Bruker\TopSpin3.5pl6} 1706 39
2.00
0.99
0.88
0.91
0.94
0.91
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
102.
05
108.
0210
8.19
122.
96
128.
77
147.
7015
0.14
167.
45
![Page 47: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/47.jpg)
S47
-3-2-1012345678910111213141516f1 (ppm)
170619.f340.10.fidKathir KM11-196PROTON DMSO {C:\Bruker\TopSpin3.5pl6} 1706 40
1.01
1.98
0.85
1.00
0.85
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
119.
09
127.
9512
9.03
131.
1113
3.18
139.
81
169.
54
![Page 48: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/48.jpg)
S48
-3-2-1012345678910111213141516f1 (ppm)
170619.f341.10.fidKathir KM11-197PROTON DMSO {C:\Bruker\TopSpin3.5pl6} 1706 41
4.36
1.00
1.00
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
127.
4712
9.14
130.
0713
0.14
131.
0213
7.60
168.
67
![Page 49: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/49.jpg)
S49
-3-2-1012345678910111213141516f1 (ppm)
170620.f331.10.fidKathir KM11-198PROTON DMSO {C:\Bruker\TopSpin3.5pl6} 1706 31
0.89
1.00
1.97
0.92
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
121.
6412
1.77
125.
2812
5.39
125.
5912
5.64
125.
6912
5.74
126.
8612
6.91
126.
9612
7.01
128.
0912
8.16
128.
2212
8.29
129.
2512
9.70
130.
1113
0.54
132.
2413
2.68
133.
1113
3.55
138.
2813
8.31
138.
3413
8.36
167.
98
![Page 50: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/50.jpg)
S50
-3-2-1012345678910111213141516f1 (ppm)
170620.f332.10.fidKathir KM11-199PROTON DMSO {C:\Bruker\TopSpin3.5pl6} 1706 32
1.92
0.64
2.70
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
115.
3811
5.66
130.
5113
0.63
131.
1813
1.22
162.
7516
6.04
167.
35
![Page 51: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/51.jpg)
S51
-3-2-1012345678910111213141516f1 (ppm)
170620.f333.10.fidKathir KM11-202PROTON DMSO {C:\Bruker\TopSpin3.5pl6} 1706 33
0.99
0.82
2.00
0.80
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
128.
3412
9.18
131.
41
140.
73
163.
44
![Page 52: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/52.jpg)
S52
-3-2-1012345678910111213141516f1 (ppm)
170620.f334.10.fidKathir KM11-205PROTON DMSO {C:\Bruker\TopSpin3.5pl6} 1706 34
3.00
1.00
1.94
1.06
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
15.7
9
127.
7213
2.04
132.
34
140.
41
164.
63
![Page 53: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/53.jpg)
S53
-3-2-1012345678910111213141516f1 (ppm)
170620.f335.10.fidKathir KM11-214PROTON DMSO {C:\Bruker\TopSpin3.5pl6} 1706 35
1.00
0.80
1.00
0.98
0.82
0.93
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
122.
37
126.
86
138.
04
148.
8615
0.73
166.
58
![Page 54: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/54.jpg)
S54
-3-2-1012345678910111213141516f1 (ppm)
170621.f356.10.fidKathir/ KM II-211PROTON DMSO {C:\Bruker\TopSpin3.5pl6} 1706 56
2.83
1.13
1.00
0.83
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
124.
3912
9.30
131.
0613
3.06
133.
78
147.
69
167.
69
![Page 55: Supporting Information Primary Amides Oxidation Process ... · Sharif, Narayana V. Kalevaru, and Rajenahally V. Jagadeesh* Leibniz-Institut für Katalyse e. V. an der Universität](https://reader034.fdocuments.in/reader034/viewer/2022051604/6000cf59d6e3931fe24beb39/html5/thumbnails/55.jpg)
S55
-3-2-1012345678910111213141516f1 (ppm)
170621.f357.10.fidKathir/ KM II-213PROTON DMSO {C:\Bruker\TopSpin3.5pl6} 1706 57
0.95
2.00
1.95
0.86
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
116.
4111
8.68
121.
1512
2.09
125.
5013
0.33
132.
15
151.
90
166.
62