Cp*RhIII-Catalyzed Directed Amidation of Aldehydes with Anthranils

Article abstract of DOI:10.1002/ejoc.201700457

An approach towards construction of amide C–N bonds under mild conditions through rhodium(III) catalysis has been explored. Previous waste-free amidations were generally limited to the condensation of carboxylic acids and amines. In this report, we directly applied amination of the aldehyde C(sp²)–H bond to extend the scope of amidation reactions. The amination shows a wide substrates scope, and several important functional groups were tolerated under the benign reaction conditions. The synthesized amides are important precursors for the preparation of benzoxazinone derivatives, found in various bioactive natural products.q.

Full text of DOI:10.1002/ejoc.201700457

A Journal of
Accepted Article
Title: Cp*Rh(III)-Catalyzed Directed Amidation of Aldehydes Using
Anthranils
Authors: Suvankar Debbarma and Modhu Sudan Maji
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10.1002/ejoc.201700457
European Journal of Organic Chemistry
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Cp*Rh(III)-Catalyzed Directed Amidation of Aldehydes Using
Anthranils
Suvankar Debbarma[a] and Modhu Sudan Maji*[a]
Abstract: An approach towards construction of amide C-N bond
under mild conditions through rhodium(III) catalysis has been
explored. Previous waste-free amidations were generally limited to
the condensation of carboxylic acids and amines. In this report, we
directly applied amination of aldehyde C(sp2)-H bond to extend the
scope of amidation reactions. Amination shows wide substrates scope
and several important functional groups were tolerated under the
benign reaction conditions. Synthesized amides are important
precursor for the preparation of benzoxazinone derivatives, found in
various bioactive natural products.
by developing chelation-assisted aldehyde C-H amination
reaction.
Introduction
Amide bonds are ubiquitous in a wide range of pharmaceuticals,
agrochemicals, and natural products.1 Amidation by
stoichiometric activation of carboxylic acid requires harsh reaction
conditions and it also produces large amount of chemical waste.2
Despite decent literature advancement, waste-free amidation is
still a major concern.3 Atom-economic construction of C-N bonds
has been perceived as one of the central topics in synthesis.4 In
this context direct C-H amination of aldehyde C(sp2)-H would be
a mild, atom-economic alternative approach. Contemporary
examples of this approach comprise N-heterocyclic carbene
Scheme 1. Bioactive molecules containing amide functional groups and
benzoxazinones.
(NHC)-catalyzed,5
metal-catalyzed,6
metal-free
oxidative
amidation of aldehydes with amines,7 the Schmidt amidation of
aldehydes with azides,8 base/acid-mediated amidation of
aldehydes with azides,8e,9 organocatalytic oxidative amidation of
aldehydes with amines using stoichiometric activation,10 and
cross-coupling of acyl and aminyl radicals.11 Albeit significant
progress has been made in the formation of amide C-N bonds, a
novel strategies for amide bond formation under mild reaction
conditions remains attractive. Transition metals have shown
significant potential in C-N bond formation using various nitrogen
sources,
such
as
azides,12
amides,13
NFSI
(N-
Fluorobenzenesulfonimide),14 1,4,2-dioxazol-5-ones,15 O-benzoyl
hydroxylmorpholine,16 sulfamate ester.17 For such synthetic
protocols significant amount of external oxidants are generally
necessary.13a To our knowledge, redox neutral C-N bond
formation via chelation-assisted directed aldehyde C-H bond
functionalization remains under developed. In our ongoing
interest in C-H bond functionalization,18 we are intended to
investigate a method to accesses amides directly from aldehydes
Scheme 2. Boronic acid and Rh(III)-catalyzed amidation reactions.
Recently, several literatures disclosed that Cp*RhIII-complexes
undergo chelation-assisted directed electrophilic metalation of
ortho-C(sp2)-H bonds to form variety of aryl/alkenyl-rhodium
complexes,19 which is coupled to a range of functional groups20
including azides,21 anthranils,22 and nitrosobenzenes.23 Owing to
the significant coordinating property and cleavable polar N-O bond,
we contemplated that anthranils may serve the purpose of
aldehydes C-H amination reaction. Particularly, this strategy
could convey a nucleophilic amino group tethered to an
electrophilic carbonyl moiety, which can be difficult to introduce.
Although direct amination of aldehyde C-H bond using azides has
been reported earlier by Y. Li and co-worker (Scheme 1a),21d no
further progress has been made so far in this field. Current
[a]
S. Debbarma, M. S. Maji
Department of Chemistry
Indian Institute of Technology Kharagpur
Kharagpur, W.B., India, PIN-721302
E-mail: msm@chem.iitkgp.ernet.in
www.chemistry.iitkgp.ac.in/~msm/
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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approach of C-H amination using anthranil is under developed
considering its high reactivity towards transition metals. Herein,
we have disclosed an efficient rhodium(III)-catalyzed direct
C(sp2)-H amination of readily accessible N-sulfonyl 2-
aminobenzaldehyde24 using anthranils under mild conditions.
such as KOAc, CuOAc, and AgOAc did not improve the yield
(entries 3 to 5). However, changing the acetate source to CsOAc
increases the yield significantly (84%, entry 6). Lowering either
the reaction temperature or catalyst loading decreases the yields
of 3aa (entries 7 to 9). Upon changing the co-catalyst to AgBF4
from AgSbF6, the yield decreases slightly (entry 10). The product
was not detected in absence of either catalyst or on using a strong
base NaOMe (entries 11 and 12).25 Among other metal catalysts
tested (entries 13 to 16), only Cp*Co(CO)I2 provided 3aa in 20%
yield (entry 14).
Results and Discussion
Table 1. Optimization of the reaction conditions for amidation reaction.[a]
With the optimized reaction conditions in hand, next we explored
the scope of this amidation reaction (Table 2). Introduction of
fluorine, chlorine, and bromine substitutions at the different
positions of 1 is well tolerated, and the products were isolated in
76–82% yields (3ba–da). Phenyl-substituted 1 also provided
amide 3ea in 82% yield. Amine protected with aliphatic sulfonyl
chloride reacted smoothly to provide products 3fa and 3ga in 74%
and 81% yields, respectively. Several other aryl and
heteroarylsulfonyl protected aldehydes were also suitable
substrates, and compounds 3ha–la were isolated in 76-88%
yields. Surprisingly, on decreasing the acidity of the N-H
functional groups by changing the protecting group of amine from
sulfonyl to acetate, pivaloyl or tert-butyloxycarbonyl, no amide
products 3ma–oa were detected.
Entry
1[c]
Catalyst, [mol-%]
[Cp*RhCl2]2, 2.5
Base [1.0 equiv] Temp [oC] Yield [%][b]
-
<5
78
80
80
[Cp*RhCl2]2, 2.5
2
NaOAc
3
4
[Cp*RhCl2]2, 2.5
[Cp*RhCl2]2, 2.5
[Cp*RhCl2]2, 2.5
[Cp*RhCl2]2, 2.5
[Cp*RhCl2]2, 2.5
[Cp*RhCl2]2, 2.5
[Cp*RhCl2]2, 2.0
[Cp*RhCl2]2, 2.5
-
KOAc
CuOAc
AgOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
NaOMe
CsOAc
CsOAc
CsOAc
CsOAc
80
80
80
80
r.t.
60
80
80
80
80
80
80
80
80
70
50
Table 2. Rh(III)-Catalyzed C-H amination of substituted N-sulfonyl 2-
aminobenzaldehyde 1 with anthranil 2a.[a]
5
66
6
84
7
20
8
62
9
82
10[d]
11[e]
12
13
14
15
16
80
nd
[Cp*RhCl2]2, 2.5
[Cp*CoCl2]2, 2.5
Cp*Co(CO)I2, 2.5
[Cp*IrCl2]2, 2.5
[(p-cymene)RuCl2]2, 2.5
nd[f]
nd
20
nd
trace
[a] Reaction conditions: 1a (0.2 mmol), 2a (1.5 equiv), [Cp*RhCl2]2 (2.5
mol-%), AgSbF6 (10 mol-%), CsOAc (1.0 equiv), DCE (1.5 mL). [b] Yields of
isolated product 3aa are given. [c] No base. [d] AgBF4 was used. [e] No
catalyst, no AgSbF6. [f] Complex reaction mixture. DCE
dichloroethane, nd = not detected.
= 1,2-
Our proof-of-concept studies were commenced with the
screening of the reaction parameters for the coupling of N-p-
toluenesulfonyl (Ts) 2-aminobenzaldehyde 1a with anthranil 2a
(Table 1). Using [Cp*RhCl2]2 as a catalyst and AgSbF6 as co-
catalyst, only traces amount of desired product 3aa was detected
(entry 1). Introduction of a base NaOAc (1.0 equiv) significantly
improved the yield of 3aa to 78% (entry 2). This result shows the
pivotal role of a base in the reaction. Varying the acetate sources
[a] Reaction conditions: 1 (0.2 mmol), 2a (1.5 equiv), [Cp*RhCl2]2 (2.5 mol-%),
AgSbF6 (10-mol%), CsOAc (1.0 equiv), DCE (1.5 mL). Isolated yields of the
products are reported.
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Further, we explored the scope of isoxazole derivatives 2 with 1a
as the reaction partner (Table 3). Isoxazole derivatives containing
substituents such as alkyl, aryl, heteroaryl, and alkenyl functional
groups were well tolerated under the reaction conditions to furnish
various substituted amides bearing a ketone functional group
3ab–aj in 75-96% yields. It is evident from the isolated yields of
amides that the reactivity of isoxazoles did not change with the
substituents. The isoxazole derivatives containing heterocyclic
ring pyridine (3af, 90%) and thiophene (3ag, 70%) also
responded well under this optimized conditions.
optimized reaction conditions, the amination of aryl aldehydes
assisted by a ortho-hydroxyl group proceeded gently with
salicylaldehyde and its derivatives as products 5a–c were isolated
in 77–83% yields. The outcome did not change much in case of
the aldehyde attached with polycyclic aromatic hydrocarbon such
as naphthalene (77%, 5d). Free hydroxyl group is necessary for
this amidation reaction as no products 5e–f were isolated upon
using ortho-methoxy benzaldehydes. This results may be due to
the consequence of low coordinating ability of methoxy group to
the transition metal complexes.
Table 3. Rh(III)-Catalyzed C-H amination of 1a with isoxazole derivatives 2.[a]
[a] Reaction conditions: 1a (0.2 mmol), 2 (1.5 equiv), [Cp*RhCl2]2 (2.5 mol-%),
AgSbF6 (10 mol-%), CsOAc (1.0 equiv), DCE (1.5 mL). Isolated yields of the
products are reported.
Scheme 3. a) Amidation of quinoline-8-carbaldehyde. b) Oxidative cyclization
of 3aa. c) Amidation reaction of 1a with 2a in gram scale.
Table 4. Rh(III)-Catalyzed C-H amination of salicylaldehydes 4 with anthranil
2a.[a]
[a] Reaction conditions: 4 (0.2 mmol), 2a (1.5 equiv), [Cp*RhCl2]2 (2.5 mol-%),
AgSbF6 (10 mol-%), CsOAc (1.0 equiv), DCE (1.5 mL). Isolated yields of the
products are reported.
Changing the directing group from sulfonamide to phenol was
also very efficient for this amidation reaction (Table 4). This
provided a unique route to protecting group free amidation
reaction for 2-hydroxy aryl aldehydes substrates. Under the same
Scheme 4. Mechanistic study and plausible mechanism.
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(multiplet); coupling constants (J) are given in Hertz (Hz). Chemical shift
for 1H NMR spectra were reported with respect to the residual signal of
CHCl3 at 7.26 ppm present in CDCl3. Chemical shifts for 13C NMR spectra
were mentioned in ppm with respect to the center of a triplet at 77.16 ppm
of chloroform-d. High-resolution mass spectra (HRMS) were recorded by
using TOF, ESI (+ Ve) method. Other chemicals were obtained from
commercial sources, and used without further purification. The substrates
N-sulfonyl 2-aminobenzaldehyde was synthesized according to the
literature reported procedure.24a,b
To extrapolate the scope of C-H amination under the same
standard conditions we have reacted aldehyde attached with
quinoline moiety 6. This quinoline-8-carbaldehyde underwent
smooth amination with anthranil 2a to provide product 7 in 78%
yield (Scheme 3a). To show the applicability of the amide product,
we exploited the reactivity of amide functional group tethered with
an electrophilic aldehyde present in 3aa. The product 3aa readily
reacted to provide oxidative cyclized product benzoxazinone
derivative 8 in 64% yield (Scheme 3b).26g Benzoxazinone is an
important heterocycle as it is found in various bioactive natural
products.26 Finally the amidation reaction was conducted in 5.0
mmol scale, and the desired product 3aa was isolated in 1.56 g
(79% yield, Scheme 3c).
To understand the reaction mechanism, we conducted
experiments with isotopically labelled solvents with substrate 1a
in the absence of anthranil 2a (Scheme 4a). We observed that
combination of additives and catalysts were essential for C−H/D
exchange of aldehyde C−H bond. Sufficient amount of H/D
scrambling in the product 1a′ supports a reversibility of C−H
activation step in the catalytic cycle. On the basis of earlier reports
Experimental Procedure for the Synthesis of Anthranil Derivatives 2
The anthranils were synthesized from the corresponding ortho-nitro aryl
aldehyde or ketones, following a known literature procedure27 with minor
modifications. In an oven dried round bottom flask equipped with a
magnetic stirring bar, substituted 2-nitroacylbenzene (10.0 mmol) was
added. Then EtOAc–MeOH (1:1; 50 mL) and SnCl2·H2O (30.0 mmol) were
added successively. The resulting reaction mixture was allowed to stir at
room temperature for 24 h. After completion, the reaction was quenched
with saturated NaHCO3 (60 mL) and the solid residue was filtered off. The
aqueous phase was extracted with EtOAc (3 × 50 mL), the combined
organic layers were dried over NaSO4 and evaporated under vacuo. The
crude residue was purified by silica gel column chromatography using
hexanes/EtOAc as eluent to provide the pure product 2.
on
chelation
assisted
rhodium(III)-catalyzed
C−H
functionalization of N-sulfonyl 2-aminobenzaldehyde24 and the
related substrate anthranils,22 we have proposed a chelation
assisted directed C−H amination (Scheme 4b). Initially, treatment
of a rhodium catalyst with AgSbF6 and CsOAc led to the formation
of reactive rhodium(III) species A, which upon reaction with 1a
affords the cyclic rhodium species B through directed C−H
functionalization. The coordination of 2a to reactive intermediate
B delivers the intermediate C, which experiences elimination of a
formyl group with concomitant formation of a nitrido species D.22
Subsequent migration-insertion of nitrene to Rh-C bond generate
a tripodal intermediate E,22 which upon protonolysis regenerate
the catalyst A along with the product 3aa.
General Procedure I (GPI): Rhodium(III) Catalyzed C-H Amination
Using Anthranils
To a mixture of N-sulfonyl 2-aminobenzaldehyde (0.2 mmol), anthranil (0.3
mmol), [(Cp*RhCl2)2] (3.1 mg, 2.5 mol-%), AgSbF6 (7.0 mg, 10 mol-%) and
CsOAc (38.4 mg, 0.2 mmol) in a 12 mL reaction tube, 1.5 mL of dry 1,2-
dichloroethane was added. The resulting reaction mixture was purged with
argon gas and allowed to stir at 80 oC for 6 h. After completion of the
reaction as indicated by TLC analysis, the crude residue was directly
loaded on a silica gel column. The column was eluted with appropriate
solvent system (ethylacetate/hexane) to obtain pure products 3aa-la, 3ab-
aj, 5a-d, and 7.
N-(2-formylphenyl)-2-(4-methylphenylsulfonamido)benzamide (3aa):
The titled compound 3aa was prepared according to the GPI and isolated
as white solid (66.3 mg, 84%). IR (KBr): 3238, 1650, 1592, 1542, 1450 cm-
Conclusions
1
1. H NMR (400 MHz, CDCl3): δ (ppm) 11.78 (s, 1H), 10.55 (s, 1H), 9.95
In conclusion, we have successfully developed a novel amidation
protocol by direct amination of aldehyde C-H bond. This mild
amidation protocol is external oxidant free. The reaction can even
be performed in presence of a bare phenolic hydroxyl functional
group. Incorporation of anthranils for this purpose as an amine
sources broaden the application of synthesized amide, which
leads to the formation of benzoxazinone derivatives, having
important pharmaceutical application.
(s, 1H), 8.77 (d, J = 8.4 Hz, 1H), 7.75–7.68 (m, 4H), 7.63 (d, J = 8.2 Hz,
2H), 7.48 (t, J = 7.8 Hz, 1H), 7.33 (t, J = 7.5 Hz, 1H), 7.21 (t, J = 7.6 Hz,
1H), 7.05 (d, J = 8.1 Hz, 2H), 2.18 (s, 3H). 13C NMR (100 MHz, CDCl3): δ
(ppm) 195.9, 167.7, 143.7, 140.4, 139.4, 136.6, 136.4, 133.3, 129.6, 127.4,
124.5, 123.9, 122.6, 122.5, 122.2, 120.2, 21.5. HRMS (ESI): calculated for
C21H19N2O4S ([M+H]+): 395.1060; found 395.1042.
4-fluoro-N-(2-formylphenyl)-2-(4-
methylphenylsulfonamido)benzamide (3ba): The titled compound 3ba
was prepared according to the GPI and isolated as white solid (67.6 mg,
82%). IR (KBr): 2924, 2854, 1650, 1590, 1545, 1340 cm-1. 1H NMR (400
MHz, CDCl3): δ (ppm) 11.91 (s, 1H), 11.10 (s, 1H), 9.96 (s, 1H), 8.78 (d, J
= 8.4 Hz, 1H), 7.82–7.78 (m, 1H), 7.76–7.69 (m, 4H), 7.48 (dd, J = 10.7,
2.5 Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.16 (d, J = 8.1 Hz, 2H), 6.89-6.85 (m,
1H), 2.28 (s, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 196.15, 167.13,
165.30 (d, J = 254.3 Hz), 144.12, 142.41 (d, J = 12.0 Hz), 140.43, 136.71,
136.44, 136.29, 129.85, 129.74, 127.43, 124.02, 122.26, 120.31, 117.09
(d, J = 3.1 Hz), 111.12 (d, J = 22.4 Hz), 108.15 (d, J = 26.4 Hz), 21.60.
HRMS (ESI): calculated for C21H17FN2NaO4S ([M+H]+): 435.0785; found
435.0794.
Experimental Section
General Procedure. All reactions were carried out in an oven dried sealed
tube under an inert atmosphere using dry solvent. Analytical thin layer
chromatography (TLC) was performed on pre-coated silica gel 60 F254
plates. Column chromatography was performed through silica gel
(100−200 mesh) using appropriate solvent system. Infrared (IR) spectra
were recorded by FTIR spectrometer and reported in cm−1. H NMR and
1
13C NMR were recorded on a (400 MHz) spectrometer in CDCl3. Data are
reported in the following order: chemical shift (δ) in ppm; multiplicities are
indicated as br (broad), s (singlet), d (doublet), t (triplet), q (quartet), m
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4-chloro-N-(2-formylphenyl)-2-(4-
7.36–7.33 (m, 2H), 7.31–7.25 (m, 2H), 7.21 (t, J = 7.6 Hz, 1H). 13C NMR
(100 MHz, CDCl3): δ (ppm) 196.0, 167.7, 140.4, 139.42, 139.36, 136.6,
136.4, 133.4, 132.9, 129.0, 127.5, 127.3, 124.5, 124.0, 122.3, 120.3.
HRMS (ESI): calculated for C20H16N2NaO4S ([M+Na]+): 403.0723; found
403.0726.
methylphenylsulfonamido)benzamide (3ca): The titled compound 3ca
was prepared according to the GPI and isolated as white solid (65.2 mg,
76%). IR (KBr): 2924, 1651, 1592, 1544, 1452, 1404 cm-1. 1H NMR (400
MHz, CDCl3): δ (ppm) 11.88 (s, 1H), 10.85 (s, 1H), 9.96 (s, 1H), 8.76 (t, J
= 7.0 Hz, 1H), 7.77–7.69 (m, 6H), 7.35 (t, J = 7.0 Hz, 1H), 7.18–7.13 (m,
3H), 2.26 (s, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 196.1, 167.0, 144.1,
141.0, 140.3, 139.6, 136.7, 136.4, 136.2, 129.8, 128.6, 127.4, 124.3, 124.1,
122.2, 121.5, 120.3, 119.8, 21.6. HRMS (ESI): calculated for
C21H18ClN2O4S ([M+H]+): 429.0670; found 429.0617.
2-(4-(tert-butyl)phenylsulfonamido)-N-(2-formylphenyl)benzamide
(3ia): The titled compound 3ia was prepared according to the GPI and
isolated as white solid (75.1 mg, 86%). IR (KBr): 2924, 1650, 1592, 1546,
1454, 1336 cm-1. 1H NMR (400 MHz, CDCl3): δ (ppm) 11.87 (s, 1H), 10.78
(s, 1H), 9.93 (s, 1H), 8.78 (d, J = 8.4 Hz, 1H), 7.78–7.67 (m, 6H), 7.48 (t, J
= 7.8 Hz, 1H), 7.32 (d, J = 8.4 Hz, 3H), 7.20 (t, J = 7.6 Hz, 1H), 1.14 (s,
9H). 13C NMR (100 MHz, CDCl3): δ (ppm) 196.1, 167.7, 156.7, 140.3,
139.6, 136.6, 136.4, 133.4, 127.4, 127.2, 126.0, 124.2, 123.9, 122.2, 122.0,
121.7, 120.2, 35.1, 31.0. HRMS (ESI): calculated for C24H25N2O4S
([M+H]+): 437.1530; found 437.1547.
5-bromo-N-(2-formylphenyl)-2-(4-
methylphenylsulfonamido)benzamide (3da): The titled compound 3da
was prepared according to the GPI and isolated as white solid (75.7 mg,
80%). IR (KBr): 2924, 1646, 1592, 1542, 1452 cm-1. H NMR (400 MHz,
CDCl3): δ (ppm) 11.78 (s, 1H), 10.36 (s, 1H), 9.96 (s, 1H), 8.71 (d, J = 8.4
Hz, 1H), 7.84 (s, 1H), 7.76 (d, J = 7.6 Hz, 1H), 7.71 (t, J = 7.9 Hz, 1H),
7.65–7.57 (m, 4H), 7.35 (t, J = 7.5 Hz, 1H), 7.07 (d, J = 8.1 Hz, 2H), 2.20
(s, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 196.0, 166.3, 143.9, 140.1,
138.3, 136.6, 136.3, 136.1, 136.0, 130.3, 129.8, 127.4, 124.3, 124.25,
124.2, 122.2, 120.2, 117.4, 21.5. HRMS (ESI): calculated for
C21H18BrN2O4S ([M+H]+): 473.0165; found 473.0140.
1
N-(2-formylphenyl)-2-(4-nitrophenylsulfonamido)benzamide
(3ja):
The titled compound 3ja was prepared according to the GPI and isolated
as white solid (75 mg, 88%). IR (KBr): 3096, 2924, 1662, 1540, 1489 cm-
1
1. H NMR (400 MHz, CDCl3): δ (ppm) 11.76 (s, 1H), 10.51 (s, 1H), 9.90
(s, 1H), 8.68 (d, J = 8.4 Hz, 1H), 8.04 (d, J = 8.8 Hz, 2H), 7.87 (d, J = 8.8
Hz, 2H), 7.78–7.69 (m, 4H), 7.56 (t, J = 7.8 Hz, 1H), 7.38–7.30 (m, 2H).
13C NMR (100 MHz, CDCl3): δ (ppm) 196.2, 167.4, 150.1, 144.9, 140.0,
138.0, 136.7, 136.6, 133.6, 128.7, 127.6, 125.9, 124.4, 124.1, 124.0, 123.9,
122.1, 120.1. HRMS (ESI): calculated for C20H15N3NaO6S ([M+Na]+):
448.0574; found 448.0571.
N-(2-formylphenyl)-4-(4-methylphenylsulfonamido)-[1,1'-biphenyl]-3-
carboxamide (3ea): The titled compound 3ea was prepared according to
the GPI and isolated as white solid (77.2 mg, 82%). IR (KBr): 2924, 2854,
1654, 1542, 1400 cm-1. 1H NMR (400 MHz, CDCl3): δ (ppm) 11.98 (s, 1H),
10.55 (s, 1H), 9.97 (s, 1H), 8.78 (d, J = 8.4 Hz, 1H), 7.99 (s, 1H), 7.81 (d,
J = 8.6 Hz, 1H), 7.76–7.65 (m, 7H), 7.47 (t, J = 7.4 Hz, 2H), 7.38–7.32 (m,
2H), 7.09 (d, J = 7.9 Hz, 2H), 2.20 (s, 3H). 13C NMR (100 MHz, CDCl3): δ
(ppm) 195.9, 167.6, 143.7, 140.4, 139.1, 138.4, 137.3, 136.6, 136.4, 131.7,
129.7, 129.2, 128.0, 127.4, 126.9, 125.9, 124.0, 122.8, 122.7, 122.2, 120.1,
21.5. HRMS (ESI): calculated for C27H23N2O4S ([M+H]+): 471.1373; found
471.1356.
N-(2-formylphenyl)-2-(naphthalene-1-sulfonamido)benzamide (3ka):
The titled compound 3ka was prepared according to the GPI and isolated
as white solid (68.9 mg, 80%). IR (KBr): 3282, 3068, 2852, 1652, 1586,
1536 cm-1. 1H NMR (400 MHz, CDCl3): δ (ppm) 11.57 (s, 1H), 11.01 (s,
1H), 9.89 (s, 1H), 8.71–8.65 (m, 2H), 8.21 (d, J = 7.4 Hz, 1H), 7.89 (d, J =
8.2 Hz, 1H), 7.72–7.65 (m, 4H), 7.60 (d, J = 7.9 Hz, 1H), 7.48 (t, J = 7.7
Hz, 1H), 7.43–7.36 (m, 2H), 7.34–7.29 (m, 2H), 7.10 (t, J = 7.6 Hz, 1H).
13C NMR (100 MHz, CDCl3): δ (ppm) 195.8, 167.6, 140.3, 139.3, 136.4,
136.2, 134.7, 134.2, 133.2, 130.3, 128.8, 128.4, 128.1, 127.3, 126.8, 124.6,
124.1, 124.0, 123.8, 122.2, 122.1, 121.5, 120.3. HRMS (ESI): calculated
for C24H19N2O4S ([M+H]+): 431.1060; found 431.1071.
N-(2-formylphenyl)-2-(methylsulfonamido)benzamide (3fa): The titled
compound 3fa was prepared according to the GPI and isolated as white
solid (47.1 mg, 74%). IR (KBr): 2924, 2854, 1668, 1590, 1544, 1452 cm-1.
1H NMR (400 MHz, CDCl3): δ (ppm) 12.21 (s, 1H), 10.81 (s, 1H), 10.00 (s,
1H), 8.85 (d, J = 8.5 Hz, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.82–7.76 (m, 2H),
7.71 (t, J = 8.0 Hz, 1H), 7.57 (t, J = 7.8 Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H),
7.29 (d, J = 7.6 Hz, 1H), 3.06 (s, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm)
196.2, 168.0, 140.5, 140.4, 136.7, 136.5, 134.0, 128.1, 124.1, 123.8, 122.4,
120.4, 120.1, 119.8, 40.1. HRMS (ESI): calculated for C15H15N2O4S
([M+H]+): 319.0747; found 319.0759.
N-(2-formylphenyl)-2-(thiophene-2-sulfonamido)benzamide (3la): The
titled compound 3la was prepared according to the GPI and isolated as
yellow solid (58.7 mg, 76%). IR (KBr): 3238, 3108, 1644, 1589, 1538, 1450
cm-1. 1H NMR (400 MHz, CDCl3): δ (ppm) 11.93 (s, 1H), 10.87 (s, 1H),
9.97 (s, 1H), 8.80 (d, J = 8.4 Hz, 1H), 7.83–7.80 (m, 2H), 7.76 (d, J = 8.9
Hz, 1H), 7.71 (t, J = 8.6 Hz, 1H), 7.56–7.49 (m, 2H), 7.38 (d, J = 5.0 Hz,
1H), 7.34 (t, J = 7.5 Hz, 1H), 7.29–7.25 (m, 1H), 6.87–6.85 (m, 1H). 13C
NMR (100 MHz, CDCl3): δ (ppm) 196.1, 167.7, 140.4, 140.1, 139.2, 136.7,
136.4, 133.5, 132.8, 132.4, 127.6, 127.3, 124.8, 124.0, 122.3, 122.2, 120.3.
GCMS (EI): m/z for C18H14N2O4S2 [M+] 386.22.
2-(butylsulfonamido)-N-(2-formylphenyl)benzamide (3ga): The titled
compound 3ga was prepared according to the GPI and isolated as white
solid (58.4 mg, 81%). IR (KBr): 3220, 2956, 2858, 1656, 1588, 1542 cm-1.
1H NMR (400 MHz, CDCl3): δ (ppm) 12.19 (s, 1H), 10.77 (s, 1H), 10.00 (s,
1H), 8.85 (d, J = 8.4 Hz, 1H), 7.95 (dd, J = 8.0, 0.9 Hz, 1H), 7.82 (d, J =
8.1 Hz, 1H), 7.77 (dd, J = 7.7, 1.5 Hz, 1H), 7.73–7.69 (m, 1H), 7.57–7.53
(m, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.27–7.23 (m, 1H), 3.16-3.12 (m, 2H),
1.84–1.76 (m, 2H), 1.42–1.33 (m, 2H), 0.84 (t, J = 7.4 Hz, 3H). 13C NMR
(100 MHz, CDCl3): δ (ppm) 196.2, 168.0, 140.6, 140.5, 136.7, 136.5, 133.9,
128.0, 124.0, 123.5, 122.4, 120.4, 119.8, 119.5, 52.1, 25.5, 21.5, 13.6.
HRMS (ESI): calculated for C18H21N2O4S ([M+H]+): 361.1217; found
361.1204.
N-(2-acetylphenyl)-2-(4-methylphenylsulfonamido)benzamide (3ab):
The titled compound 3ab was prepared according to the GPI and isolated
as white solid (78.4 mg, 96%). IR (KBr): 2924, 1640, 1592, 1539, 1456,
1342 cm-1. 1H NMR (400 MHz, CDCl3): δ (ppm) 12.47 (s, 1H), 10.68 (s,
1H), 8.80 (d, J = 8.1 Hz, 1H), 7.97 (d, J = 7.5 Hz, 1H), 7.73 (t, J = 7.6 Hz,
2H), 7.65 (d, J = 7.3 Hz, 3H), 7.46 (t, J = 7.2 Hz, 1H), 7.22–7.18 (m, 2H),
7.07 (d, J = 7.1 Hz, 2H), 2.71 (s, 3H), 2.20 (s, 3H). 13C NMR (100 MHz,
CDCl3): δ (ppm) 203.5, 167.7, 143.6, 140.7, 139.5, 135.6, 133.1, 132.0,
129.6, 127.5, 127.4, 124.3, 123.4, 122.8, 122.23, 122.17, 121.1, 28.7, 21.5.
HRMS (ESI): calculated for C22H21N2O4S ([M+H]+): 409.1217; found
409.1225.
N-(2-formylphenyl)-2-(phenylsulfonamido)benzamide (3ha): The titled
compound 3ha was prepared according to the GPI and isolated as white
solid (57.8 mg, 76%). IR (KBr): 3236, 2872, 1674, 1618, 1546, 1448 cm-1.
1H NMR (400 MHz, CDCl3): δ (ppm) 11.82 (s, 1H), 10.70 (s, 1H), 9.95 (s,
1H), 8.77 (d, J = 8.4 Hz, 1H), 7.78-7.68 (m, 6H), 7.48 (t, J = 7.8 Hz, 1H),
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10.1002/ejoc.201700457
European Journal of Organic Chemistry
FULL PAPER
N-(2-benzoylphenyl)-2-(4-methylphenylsulfonamido)benzamide
(3ac): The titled compound 3ac was prepared according to the GPI and
isolated as white solid (86.6 mg, 92%). IR (KBr): 2924, 1626, 1582, 1536,
1452, 1340 cm-1. 1H NMR (400 MHz, CDCl3): δ (ppm) 11.72 (s, 1H), 10.75
(s, 1H), 8.70 (d, J = 8.1 Hz, 1H), 7.74–7.61 (m, 9H), 7.51 (t, J = 7.2 Hz,
2H), 7.45 (t, J = 7.6 Hz, 1H), 7.21–7.15 (m, 2H), 7.09 (d, J = 7.6 Hz, 2H),
2.16 (s, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 200.3, 167.4, 143.7,
140.3, 139.5, 138.6, 136.5, 134.8, 134.2, 133.2, 132.9, 130.0, 129.6, 128.6,
127.41, 127.36, 124.3, 123.4, 123.1, 122.3, 122.0, 121.8, 21.4. HRMS
(ESI): calculated for C27H23N2O4S ([M+H]+): 471.1373; found 471.1379.
MHz, CDCl3): δ (ppm) 12.43 (s, 1H), 10.69 (s, 1H), 8.77 (d, J = 8.4 Hz, 1H),
8.07 (d, J = 8.0 Hz, 1H), 7.86 (d, J = 15.5 Hz, 1H), 7.78 (d, J = 7.9 Hz, 1H),
7.74 (d, J = 8.3 Hz, 1H), 7.68–7.61 (m, 6H), 7.49–7.45 (m, 4H), 7.28 (d, J
= 7.9 Hz, 1H), 7.22 (d, J = 7.8 Hz, 1H), 7.06 (d, J = 8.1 Hz, 2H), 2.17 (s,
3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 193.6, 167.5, 146.3, 143.7,
140.8, 139.3, 136.3, 135.12, 133.05, 131.3, 130.9, 129.6, 129.2, 128.8,
127.44, 127.36, 124.5, 123.6, 123.4, 123.0, 122.4, 122.3, 121.4, 21.5.
HRMS (ESI): calculated for C29H25N2O4S ([M+H]+): 497.1530; found
497.1504.
(E)-N-(2-(3-(4-methoxyphenyl)acryloyl)phenyl)-2-(4-
N-(2-(4-(tert-butyl)benzoyl)phenyl)-2-(4-
methylphenylsulfonamido)benzamide (3ai): The titled compound 3ai
was prepared according to the GPI and isolated as yellow solid (88.5 mg,
84%). IR (KBr): 2924, 2854, 1638, 1580, 1510, 1338 cm-1. 1H NMR (400
MHz, CDCl3): δ (ppm) 12.50 (s, 1H), 10.72 (s, 1H), 8.74 (d, J = 8.4 Hz, 1H),
8.05 (d, J = 7.9 Hz, 1H), 7.85–7.72 (m, 3H), 7.64–7.61 (m, 5H), 7.52–7.44
(m, 2H), 7.26–7.20 (m, 2H), 7.05 (d, J = 8.0 Hz, 2H), 6.95 (d, J = 8.3 Hz,
2H), 3.86 (s, 3H), 2.15 (s, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 193.5,
167.4, 162.3, 146.3, 143.7, 140.7, 139.3, 136.4, 134.8, 133.0, 130.7, 129.6,
127.5, 127.4, 127.3, 124.5, 123.9, 123.4, 123.1, 122.4, 121.4, 119.9, 119.8,
114.7, 55.6, 21.5. HRMS (ESI): calculated for C30H27N2O5S ([M+H]+):
527.1635; found 527.1611.
methylphenylsulfonamido)benzamide (3ad): The titled compound 3ad
was prepared according to the GPI and isolated as pale yellow solid (80
mg, 75%). IR (KBr): 2978, 1622, 1582, 1532, 1450, 1340 cm-1. H NMR
(400 MHz, CDCl3): δ (ppm) 11.66 (s, 1H), 10.73 (s, 1H), 8.67 (d, J = 8.3
Hz, 1H), 7.74–7.65 (m, 8H), 7.52 (d, J = 8.3 Hz, 2H), 7.45 (t, J = 7.5 Hz,
1H), 7.21–7.14 (m, 2H), 7.08 (d, J = 8.1 Hz, 2H), 2.15 (s, 3H), 1.37 (s, 9H).
13C NMR (100 MHz, CDCl3): δ (ppm) 199.9, 167.3, 156.9, 143.7, 140.0,
139.5, 136.4, 135.7, 134.5, 134.0, 133.2, 130.2, 129.6, 127.4, 127.4, 125.6,
124.3, 123.9, 123.0, 122.4, 122.1, 121.8, 35.3, 31.2, 21.4. HRMS (ESI):
calculated for C31H31N2O4S ([M+H]+): 527.1999; found 527.2016.
1
N-(2-(2-naphthoyl)phenyl)-2-(4-
(E)-N-(2-(3-(4-chlorophenyl)acryloyl)phenyl)-2-(4-
methylphenylsulfonamido)benzamide (3ae): The titled compound 3ae
was prepared according to the GPI and isolated as yellow solid (85.4 mg,
82%). IR (KBr): 2924, 2854, 1628, 1580, 1534, 1454 cm-1. 1H NMR (400
MHz, CDCl3): δ (ppm) 11.71 (s, 1H), 10.78 (s, 1H), 8.72 (d, J = 8.1 Hz, 1H),
8.20 (s, 1H), 7.98–7.93 (m, 3H), 7.83 (d, J = 8.3 Hz, 1H), 7.75–7.57 (m,
8H), 7.45 (t, J = 7.5 Hz, 1H), 7.23–7.15 (m, 2H), 7.09 (d, J = 7.6 Hz, 2H),
2.15 (s, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 200.2, 167.4, 143.8,
140.2, 139.6, 136.4, 135.7, 135.4, 134.7, 134.2, 133.2, 132.2, 131.9, 129.6,
129.5, 128.8, 128.6, 128.0, 127.41, 127.36, 127.3, 125.6, 124.3, 123.9,
123.2, 122.2, 121.9, 121.86, 21.4. HRMS (ESI): calculated for
C31H25N2O4S ([M+H]+): 521.1530; found 521.1541.
methylphenylsulfonamido)benzamide (3aj): The titled compound 3aj
was prepared according to the GPI and isolated as yellow solid (86 mg,
81%). IR (KBr): 3076, 2924, 1636, 1584, 1520, 1336 cm-1. 1H NMR (400
MHz, CDCl3): δ (ppm) 12.40 (s, 1H), 10.70 (s, 1H), 8.77 (d, J = 8.4 Hz, 1H),
8.05 (d, J = 7.4 Hz, 1H), 7.82–7.77 (m, 2H), 7.73 (d, J = 8.3 Hz, 1H), 7.69–
7.64 (m, 3H), 7.62–7.58 (m, 3H), 7.47 (t, J = 7.4 Hz, 1H), 7.42 (d, J = 8.4
Hz, 2H), 7.29–7.26 (m, 1H), 7.24–7.20 (m, 1H), 7.07 (d, J = 8.1 Hz, 2H),
2.17 (s, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 193.4, 167.5, 144.8,
143.7, 140.9, 139.5, 137. 2, 136.5, 135.3, 133.11, 133.07, 130.9, 129.9,
129.62, 129.57, 127.5, 127.4, 124.4, 123.5, 123.4, 122.8, 122.8, 122.3,
121.5, 21.5. HRMS (ESI): calculated for C29H24ClN2O4S ([M+H]+):
531.1140; found 531.1109.
2-(4-methylphenylsulfonamido)-N-(2-picolinoylphenyl)benzamide
(3af): The titled compound 3af was prepared according to the GPI and
isolated as white solid (84.9 mg, 90%). IR (KBr): 3064, 2924, 1644, 1584,
1536, 1454 cm-1. 1H NMR (400 MHz, CDCl3): δ (ppm) 11.92 (s, 1H), 10.68
(s, 1H), 8.75 (d, J = 8.3 Hz, 2H), 7.95–7.87 (m, 3H), 7.75 (d, J = 8.1 Hz,
2H), 7.70–7.63 (m, 3H), 7.54–7.51 (m, 1H), 7.46 (t, J = 7.8 Hz, 1H), 7.20
(q, J = 7.1 Hz, 2H), 7.08 (d, J = 7.9 Hz, 2H), 2.15 (s, 3H). 13C NMR (100
MHz, CDCl3): δ (ppm) 197.8, 167.4, 155.8, 148.9, 143.8, 141.1, 139.4,
137.3, 136.4, 135.4, 135.3, 133.1, 129.6, 127.4, 127.3, 126.3, 124.8, 124.4,
123.0, 122.7, 122.3, 121.9, 121.3, 21.4. HRMS (ESI): calculated for
C26H22N3O4S ([M+H]+): 472.1326; found 472.1342.
N-(2-formylphenyl)-2-hydroxybenzamide (5a): The titled compound 5a
was prepared according to the GPI and isolated as white solid (37 mg,
77%). IR (KBr): 2924, 1762, 1654, 1590, 1548, 1454 cm-1. 1H NMR (400
MHz, CDCl3): δ (ppm) 12.23 (s, 1H), 12.11 (s, 1H), 9.97 (s, 1H), 8.81 (d, J
= 8.4 Hz, 1H), 7.84 (d, J = 7.9 Hz, 1H), 7.73 (d, J = 7.5 Hz, 1H), 7.66 (t, J
= 7.8 Hz, 1H), 7.46 (t, J = 7.7 Hz, 1H), 7.30–7.26 (m, 1H), 7.03–6.97 (m,
2H). 13C NMR (100 MHz, CDCl3): δ (ppm) 196.1, 169.8, 162.5, 140.4,
136.5, 136.4, 135.1, 126.48, 123.7, 122.3, 120.4, 119.5, 118.9, 114.8.
HRMS (ESI): calculated for C14H12NO3 ([M+H]+): 242.0812; found
242.0814.
2-(4-methylphenylsulfonamido)-N-(2-(thiophene-2-
N-(2-formylphenyl)-2-hydroxy-5-methylbenzamide (5b): The titled
compound 5b was prepared according to the GPI and isolated as white
solid (41 mg, 81%). IR (KBr): 3262, 2852, 1656, 1588, 1548, 1456 cm-1.
1H NMR (400 MHz, CDCl3): δ (ppm) 12.16 (br s, 1H), 11.90 (s, 1H), 9.96
(s, 1H), 8.79 (d, J = 8.5 Hz, 1H), 7.71 (d, J = 7.6 Hz, 1H), 7.64 (t, J = 7.9
Hz, 1H), 7.59 (s, 2H), 7.29–7.25 (m, 2H), 6.91 (d, J = 8.4 Hz, 1H), 2.37 (s,
3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 196.0, 169.8, 160.3, 140.5,
136.41, 136.36, 136.0, 128.6, 126.3, 123.6, 122.3, 120.4, 118.6, 114.3,
20.9. GCMS (EI): m/z for C15H13NO3 [M+] 255.07.
carbonyl)phenyl)benzamide (3ag): The titled compound 3ag was
prepared according to the GPI and isolated as yellow solid (66.7 mg, 70%).
1
IR (KBr): 2924, 2854, 1654, 1580, 1524, 1449 cm-1. H NMR (400 MHz,
CDCl3): δ (ppm) 11.19 (s, 1H), 10.73 (s, 1H), 8.60 (d, J = 8.4 Hz, 1H), 7.92
(d, J = 7.8 Hz, 1H), 7.79 (d, J = 4.8 Hz, 1H), 7.73–7.63 (m, 6H), 7.45 (t, J
= 7.8 Hz, 1H), 7.28–7.24 (m, 1H), 7.21–7.16 (m, 2H), 7.08 (d, J = 8.0 Hz,
2H), 2.16 (s, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 190.4, 167.1, 143.8,
143.7, 139.5, 139.1, 136.4, 136.0, 135.4, 134.2, 133.2, 132.4, 129.6, 128.4,
127.3, 124.5, 124.3, 123.4, 122.1, 121.9, 21.4. HRMS (ESI): calculated for
C25H21N2O4S2 ([M+H]+): 477.0937; found 477.0957.
N-(2-formylphenyl)-2-hydroxy-5-iodobenzamide (5c): The titled
compound 5c was prepared according to the GPI and isolated as white
solid (61 mg, 83%). IR (KBr): 3240, 2844, 1641, 1610, 1576, 1546 cm-1.
1H NMR (400 MHz, CDCl3): δ (ppm) 12.26 (br s, 1H), 12.07 (s, 1H), 10.01
(s, 1H), 8.78 (d, J = 8.4 Hz, 1H), 8.14 (s, 1H), 7.77 (d, J = 8.9 Hz, 1H),
7.72–7.67 (m, 2H), 7.33 (t, J = 7.4 Hz, 1H), 6.81 (d, J = 8.7 Hz, 1H). 13C
(E)-N-(2-cinnamoylphenyl)-2-(4-
methylphenylsulfonamido)benzamide (3ah): The titled compound 3ah
was prepared according to the GPI and isolated as yellow solid (75.5 mg,
76%). IR (KBr): 3066, 2922, 1644, 1582, 1518, 1446 cm-1. 1H NMR (400
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10.1002/ejoc.201700457
European Journal of Organic Chemistry
FULL PAPER
NMR (100 MHz, CDCl3): δ (ppm) 196.2, 168.5, 162.1, 143.5, 140.2, 136.6,
136.4, 135.3, 124.1, 122.4, 121.3, 120.5, 117.2, 80.3. GCMS (EI): m/z for
C14H10INO3 [M+] 366.94.
[2]
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a) C. A. G. N. Montalbetti, V. Falque, Tetrahedron 2005, 61, 10827; b) E.
Valeur, M. Bradely, Chem. Soc. Rev. 2009, 38, 606; c) J. R. Dunetz, J.
Magano, G. A. Weisenburger, Org. Process Res. Dev. 2016, 20, 140.
For selected references on waste-free-amidation, see: a) K. Ishihara, S.
Ohara, H. Yamamoto, J. Org. Chem. 1996, 61, 4196; b) T. Maki, K.
Ishihara, H. Yamamoto, Tetrahedron 2007, 63, 8645; c) C. Gunanathan,
Y. Ben-David, D. Milstein, Science 2007, 317, 790; d) R. M. Al-Zoubi, O.
Marion, D. G. Hall, Angew. Chem. Int. Ed. 2008, 47, 2876; e) K. Arnold,
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f) R. M. d. Figueiredo, J.-S. Suppo, J.-M. Campagne, Chem. Rev. 2016,
116, 12029.
N-(2-formylphenyl)-2-hydroxy-1-naphthamide
(5d):
The
titled
compound 5d was prepared according to the GPI and isolated as white
solid (45 mg, 77%). IR (KBr): 3234, 2924, 1674, 1576, 1508, 1450 cm-1.
1H NMR (400 MHz, CDCl3): δ (ppm) 12.09 (s, 1H), 11.00 (s, 1H), 9.88 (s,
1H), 8.95 (d, J = 8.8 Hz, 1H), 8.31 (d, J = 8.6 Hz, 1H), 7.89 (d, J = 9.0 Hz,
1H), 7.84 (d, J = 8.0 Hz, 1H), 7.75–7.71 (m, 2H), 7.56 (t, J = 7.7 Hz, 1H),
7.43 (t, J = 7.5 Hz, 1H), 7.34 (t, J = 7.5 Hz, 1H), 7.21 (d, J = 9.0 Hz, 1H).
13C NMR (100 MHz, CDCl3): δ (ppm) 195.2, 169.9, 160.1, 140.2, 136.33,
136.27, 135.0, 130.4, 129.3, 129.1, 128.1, 124.1, 123.9, 123.7, 122.5,
121.0, 119.3, 110.7. HRMS (ESI): calculated for C18H13NNaO3 ([M+Na]+):
314.0788; found 314.3045.
[4]
[5]
a) T. E. Mîller, M. Beller, Chem. Rev. 1998, 98, 675; b) J. F. Hartwig, Acc.
Chem. Res. 2008, 41, 1534; c) D. S. Surry, S. L. Buchwald, Angew.
Chem. Int. Ed. 2008, 47, 6338; d) J. Bariwal, E. Van der Eycken, Chem.
Soc. Rev. 2013, 42, 9283; e) K. Shin, H. Kim, S. Chang, Acc. Chem. Res.
2015, 48, 1040; f) X. Wang, T. Gensch, A. Lerchen, C. G. Daniliuc, F.
Glorius, J. Am. Chem. Soc. 2017, 139, 6506; g) A. P. Smalley, J. D.
Cuthbertson, M. J. Gaunt, J. Am. Chem. Soc. 2017, 139, 1412.
a) H. U. Vora, T. Rovis, J. Am. Chem. Soc. 2007, 129, 13796; b) J. W.
Bode, S. S. Sohn, J. Am. Chem. Soc. 2007, 129, 13798; c) B. E. Maki,
K. A. Scheidt, Org. Lett. 2008, 10, 4331; d) B. E. Maki, A. Chan, E. M.
Phillips, K. A. Scheidt, Tetrahedron 2009, 65, 3102; e) S. De Sarkar, A.
Studer, Org. Lett. 2010, 12, 1992; f) S. Kuwano, S. Harada, R. Oriez, K.
Yamada, Chem. Commun. 2012, 48, 145; g) P. Wheeler, H. U. Vora, T.
Rovis, Chem. Sci. 2013, 4, 1674; h) S. Premaletha, A. Ghosh, S. Joseph,
S. R. Yetra, A. T. Biju, Chem. Commun. 2017, 53, 1478.
N-(2-formylphenyl)quinoline-8-carboxamide (7): The titled compound 7
was prepared according to the GPI and isolated as white solid (43 mg,
1
78%). IR (KBr): 2924, 1680, 1572, 1520, 1448 cm-1. H NMR (400 MHz,
CDCl3): δ (ppm) 14.40 (s, 1H), 10.14 (s, 1H), 9.17 (dd, J = 4.1, 1.7 Hz, 1H),
8.93 (d, J = 8.4 Hz, 1H), 8.82 (dd, J = 7.4, 1.3 Hz, 1H), 8.27 (dd, J = 8.3,
1.4 Hz, 1H), 7.99 (d, J = 8.1 Hz, 1H), 7.76 (dd, J = 7.6, 1.4 Hz, 1H), 7.70–
7.62 (m, 2H), 7.53 (dd, J = 8.3, 4.2 Hz, 1H), 7.28–7.24 (m, 1H). 13C NMR
(100 MHz, CDCl3): δ (ppm) 193.0, 165.6, 149.7, 145.3, 140.1, 137.4, 135.5,
135.0, 134.2, 132.5, 129.9, 128.4, 126.6, 125.1, 123.5, 122.7, 121.5.
HRMS (ESI): calculated for C17H12N2NaO2 ([M+Na]+): 299.0791; found
299.1794.
[6]
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carried out according to the literature report26g with slight modification. To
a suspension of amide 3aa (39.5 mg, 0.1 mmol) and CoCl2 (1.3 mg, 0.01
mmol) in MeCN (0.5 mL) was added TBHP (1.0 mmol) dropwise at room
temperature over a period of 3 min. The reaction mixture was then heated
at reflux for 8 h and monitored by TLC analysis. After completion of the
reaction solvent was evaporated under reduced pressure, and purified by
flash column chromatography using ethylacetate/hexane as eluent. The
compound 8 was isolated as white solid (25 mg, 64%). IR (KBr): 2926,
1778, 1604, 1570, 1468 cm-1. 1H NMR (400 MHz, CDCl3): δ (ppm) 12.20
(s, 1H), 8.24 (dd, J = 7.9, 1.0 Hz, 1H), 8.15 (dd, J = 8.1, 1.3 Hz, 1H). 7.91
(t, J = 7.7 Hz, 1H), 7.78–7.68 (m, 4H), 7.60 (t, J = 7.7 Hz, 1H), 7.47 (t, J =
7.8 Hz, 1H), 7.16–7.13 (m, 3H), 2.32 (s, 3H). 13C NMR (100 MHz, CDCl3):
δ (ppm) 158.1, 157.2, 145.1, 144.1, 139.9, 137.3, 136.6, 134.1, 129.82,
129.76, 129.3, 128.9, 127.3, 126.8, 123.5, 119.8, 116.7, 115.7, 21.6.
HRMS (ESI): calculated for C21H17N2O4S ([M+H]+): 393.0904; found
392.9594.
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C-H Bond Functionalization;
Amidation
Suvankar Debbarma, Modhu Sudan
Maji*
Page No. – Page No.
Cp*Rh(III)-Catalyzed Directed
Amidation of Aldehydes Using
Anthranils
A novel synthetic route for the construction of amide C-N bonds under chelation assisted Cp*Rh(III)-catalyzed C-H bond
functionalization has been developed. This allows an easy access to starting precursors for the synthesis of 4H-benzoxazin-4-
one derivative.
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