Visible-Light-Induced Direct Oxidative C?H Amidation of Heteroarenes with Sulfonamides

Article abstract of DOI:10.1002/chem.201604014

A direct oxidative C?H amidation of heteroarenes with sulfonamides via nitrogen-centered radicals has been achieved. Nitrogen-centered radicals are directly generated from oxidative cleavage of N?H bonds under visible-light photoredox catalysis. Sulfonami

Full text of DOI:10.1002/chem.201604014

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Accepted Article
Title: Visible-Light-Induced Direct Oxidative CH Amidation of Heteroarenes with Sul-
fonamides
Authors: Kun Tong; Xiaodong Liu; Yan Zhang; Shouyun Yu
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Visible-Light-Induced Direct Oxidative C−H Amidation of
Heteroarenes with Sulfonamides**
Kun Tong,[a] Xiaodong Liu,[a] Yan Zhang,*[a] and Shouyun Yu *[a]
Abstract: A direct oxidative C−H amidation of heteroarenes with
sulfonamides via nitrogen-centered radicals has been achieved.
Nitrogen-centered radicals are directly generated from oxidative
cleavage of NH bonds under visible-light photoredox catalysis.
Sulfonamides, which are easily accessed, are used as tunable
nitrogen sources and bleach (aqueous NaClO solution) is used
as the oxidant. A variety of heteroarenes, including indoles,
pyrroles and benzofurans, can undergo this amidation with high
yields (up to 92%). These reactions are highly regioselective,
and all the products are isolated as single regioisomer.
light-induced oxidative CH amination of (hetero)arenes via
arene cation radicals using nonactivated N-heterocyles as
nucleophiles (Figure 1b). Very recently, Knowles[14] and Xiao[15]
reported that direct cleavage of strong N–H bond to generate of
NCRs by oxidative proton-coupled electron transfer (PCET) or
oxidative deprotonation electron transfer (ODET), which allowed
radical cascade reactions for N-heterocycle synthesis. Inspired
by these work, as well as our research interests on visible-light-
mediated NCR chemistry,[16-17] we sought to develop a direct
oxidative CH amidation of (hetero)arenes with nonactivated
sulfonamides under photoredox catalysis[18] (Figure 1c).
The installation of nitrogen atom into organic molecules has
been of intensive research interest in synthetic, material and
medicinal chemistry.[1] As important structural fragments, these
aminated products often exhibit significant biological
properties.[2] The most classic method for CN bond formation is
copper-promoted Ullman coupling of aryl halides with amines.[3]
Palladium-catalyzed Buchwald−Hartwig amination/amidation of
aryl or vinyl (pseudo)halides with amines (amides) have recently
emerged as valuable synthetic tools for C−N bond formation.[4]
Copper-catalyzed and ligand-accelerated variations have also
been achieved, which are good alternatives for the synthesis of
vinyl or aryl amines.[5] However, these procedures usually need
elevated temperature, pre-functionalized substrates, e. g.
halides or pseudohalides and also provide stoichiometric halide
salts as by-products requiring stoichiometric base to facilitate the
reaction. The most desirable but challenging CN bond
formation strategy is direct oxidative CH amination of
hydrocarbons with amines.[6] Although some significant
contributions have been reported,[7] this attractive strategy still
suffers from some disadvantages, including harsh reaction
conditions, stoichiometric oxidants, and directing groups.
Therefore, the development of efficient and practical direct C−H
amination/amidation is still highly desirable and valuable.
Nitrogen-centered radicals (NCRs) has aroused increasing
concern in synthetic community.[8] Visible-light-induced CH
amidation of (hetero)arenes via NCRs has emerged as an
attractive strategy for CN bond formation (Figure 1a).[9-12] One
of disadvantages of these known methods is that photolabile
handles are preinstalled on the precurssors of NCRs, such as
hydroxyamine derivatives,[9] acyl azides,[10] N-haloamides,[11] and
N-aminopyridiniums.[12] Nicewicz[13a] and Xia[13b] reported visible-
Figure 1. Visible-light-induced C-H amidation of (hetero)arenes.
Our initial efforts toward this goal focused on the use of N-
methylindole (1a) and N-methyl-para-toluenesulfonamide (2a)
as coupling partners. The photocatalyst Ir(ppy)2(dtbbpy)PF6 (I)
and bleach (aqueous NaClO solution) were chosen as the
catalyst and oxidant respectively. When a solution of 1a and 2a
in CH3CN was irradiated by white LED strips in the presence of
Ir(ppy)2(dtbbpy)PF6 (I) and bleach for 30 min, the desired 2-
amidated indole 3a was isolated in 62% yield as single
regioisomer (Table 1, entry 1). Other photocatalysts, such as
Ir(dFCF3ppy)2(dtbbpy)PF6 (II), fac-Ir(ppy)3 (III), Ru(bpy)3Cl2 (IV),
Ru(bpy)3(PF6)2 (V), and Ru(phen)3(PF6)2 (VI), could not give
[a]
K. Tong, X. Liu, Prof. Dr. Y. Zhang, Prof. Dr. S. Yu
State Key Laboratory of Analytical Chemistry for Life Science ,
School of Chemistry and Chemical Engineering, Nanjing University,
Nanjing 210023 (China)
E-mail: yushouyun@nju.edu.cn (SY); njuzy@nju.edu.cn (YZ)
Homepage: http://hysz.nju.edu.cn/yusy/ (SY)
http://hysz.nju.edu.cn/yanzhang/ (YZ)
[] Financial support from the National Natural Science Foundation of
China (21472084, 21572102, and 81421091) is acknowledged.
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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improved results (entries 2−6). A variety of solvents were then
tested (entries 7−16). To our delight, a 81% yield was achieved
when 1,4-dioxane was used as the solvent (entry 16). Control
experiments verified the necessity of irradiation, and
photocatalyst (entries 17−18).
compatible in this transformation (45% for 3r). Amidated pyrrole
and benzofuran derivatives were also accessible by means of
this method to give the corresponding amidated pyrroles 3s−u
and benzofurans 3v−w with acceptable yields (46−81%). To
demonstrate the practicability of this method, we subsequently
conducted this intramolecular amidation on a gram scale. When
1.23 g of melatonin-derived indole 1k was subjected to standard
conditions, a comparative isolated yield of amidated melatonin
derivative 3k (74%, 1.59 g) was achieved. It is worth noting that
all the amidated products were isolated in single regioisomer.
Table 1. Optimization of reaction conditions.[a]
Entry
1
Photocatalyst
Solvent
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
MeOH
Yield (%)[b]
62
I
2
II
40
3
III
51
4
IV
51
5
V
54
6
VI
50
7
I
23
8
I
DMF
46
9
I
THF
62
10
11
12
13
14
15
16
17
18[c]
I
DMSO
NR
NR
57
I
acetone
t-BuOH
DCE
I
I
38
I
THP
44
I
MTBE
41
I
none
I
1,4-dioxane
1,4-dioxane
1,4-dioxane
81
trace
trace
[a] Reaction conditions: A solution of 1a (0.1 mmol, 1.0 equiv), 2a (0.2 mmol,
2.0 equiv), NaClO (aq., 0.3 mmol, 3.0 equiv), and photocatalyst (0.002 mmol,
2 mol %) in 1,4-dioxane (2.0 mL) was irradiated with 5 W white LEDs for 30
min. [b] Isolated yield. [c] No irradiation. NR = no reaction.
In order to explore the scope of this transformation under the
established optimized conditions, a variety of heteroarenes were
amidated with N-methyl-p-toluenesulfonamide (2a) (Scheme 1).
It was found that indoles bearing various substituents at the
C4−C7 positions gave 2-amidated indole derivatives 3a−f with
satisfactory yields (70−85%). C3-substituted indoles could
undergo this transformation smoothly. 3-Benzyl and 3-phenyl
indole derivatives could give 2-amidated indoles 3g and 3h in
reanonable yields (65% and 74% respectively). More biologically
important indole derivatives, such as indole propanoic acid,
tryptamine and melatonin derivatives, could also be amidated
under the identical conditions to give the corresponding
amidated indoles 3i−k with 74−88% yields. The substituents at
the N1 position were also explored. N-Methyl (Me), benzyl (Bn),
phenyl (Ph), para-methoxyphenyl (PMB), and allyl indoles
worked quite well to give the desired products 3l−p in decent
yields (81−92%). N-Boc indole could be also amidated with
slightly lower yields (62% for 3q ). 7-Azaindole derivative was
Scheme 1. C−H amidation of different heteroarenes. Reaction conditions: A
solution of 1 (0.1 mmol, 1.0 equiv), 2a (0.2 mmol, 2.0 equiv), NaClO (aq., 0.3
mmol, 3.0 equiv), and photocatalyst I (0.002 mmol, 2 mol %) in 1,4-dioxane
(2.0 mL) was irradiated with 5 W white LEDs for 1 h. The yields are for the
isolated products. [a] 4.0 equivs of 2a were used for 4 h. [b] The reaction was
run in 5.0 mmol scale.
We next sought to establish the scope of the sulfonamide
coupling partners with indole 1l in this reaction (Scheme 2). We
were pleased find that these mild photoxidative conditions
accommodated a wide range of sulfonamides. Different aromatic
sulfonamides can serve as coupling partners to give the
corresponding amidated indoles 4a-4d with 66−78% yields.
Aliphatic sulfonamides, such as trifluoromethyl (CF3), benzyl
(Bn), n-pentyl, cyclopropyl, and even styryl groups, could also
undergo this transformation in 45−89% yields (4e-4i).
Heterocyclic sulfonyl groups (furan and pyridine) could also give
amidation products 4j (90% yield) and 4k (64% yield)
respectively. N-alkyl substituents on sulfonamides were next
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explored. N-phenyl, N-benzyl and N-pentyl sulfonamides worked
quite well to give the desired products 4l-4n in decent yields (76-
89% yields). Functionalized N-alkyl groups, such as ether,
carbomate, phenol ether, benzofuran, ester, olefin and alkyne,
were also worked well to furnish the amidation products 4n-4u in
41-83% yields. Moreover, several heterocycle-fused 2-amidated
indole derivatives, typified by tetrahydropyrrolo[2,3-b]indole 4v,
To better understand the mechanism of this transforamtion, a
series of control reactions were conducted, as shown in Scheme
3. First, NCR
methylphenol (BHT) (Scheme 3a). When
6
could be trapped by 2,6-di-tert-butyl-4-
mixture of
a
sulfonamide 2a and BHT was subjected to the standard
photoxidative conditions, trapping product 5 was isolated in very
good yield no matter that indole 1a was present or not. Given
that benzyl radical B can be fromed from oxygen-centered
radical A through an intramolecular radical transfer,[19] it is
envisaged that trapping product 5 was generated by the
coupling of NCR 6 with radical B. It is known that treatment of
sulfonamide 2a with NaClO can give N-chlorosulfonamide 7,[20]
which can served as the precurssor of NCR.[11] A series of
control reactions were designed to explore this possibility. As
shown in Scheme 3b, when preformed N-chlorosulfonamide 7
was subjected to the standard conditions instead of sulfonamide
2a, no amidation product 3a was observed. Instead,
chloroamidation product 8 was isolated in 40% yield. And
chlorination product 9 was obtained in 16% GC yield if NaClO
was absent. Furthermore, coupling of indole 1l with N-
chlorosulfonamide 7 under the standard photooxidative
dihydroindolo[2,3-b]quinolines
4w,
enzo-[4,5]imidazo[1,2-
a]indole 4x, and dihydroindolo[2,1-b]quinazoline 4y, could been
constructed in 50-80% yields by intramolecular C2-amidative
cyclization of indoles.
Scheme 2. C−H amidation with different sulfonamides. Reaction condition: A
solution of 1l (0.1 mmol, 1.0 equiv), 2 (0.2 mmol, 2.0 equiv), NaClO (aq., 0.3
mmol, 3.0 equiv), and photocatalyst I (0.002 mmol, 2 mol %) in 1,4-dioxane
(2.0 mL) was irradiated with 5 W white LEDs for 30min. The yields are for the
isolated products. [a] 2.0 equivs of NaClO (0.2 mmol) were used.
Scheme 3. Mechanism Studies. The yields are for the isolated products.
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conditions gave oxidative chlorination product 10 in 41% yield.
No amidation product 3l was observed. These phenomena
suggest that N-centred radical 6 is not generated from N-
chlorosulfonamide 7.
In order to determine the quencher of the excited
photocatalyst, the fluorescence quenching [1]experiments and
Stern-Volmer analysis were performed (Figure 2a). It was
observed that the fluorescence intensity of Ir(ppy)2(dtbbpy)PF6
(I) decreased with increasing concentration of NaClO (Figure 2a)
while the fluorescence intensity kept unchanged with increasing
concentration of 2a (Figure 2b). A linear relationship between I0/I
and the concentration of NaClO was observed at low
concentrations (I0 and I are the fluorescence intensities before
and after the addition of NaClO, Figure 2d). These results
strongly suggest that the photoexcited catalyst I was quenched
by NaClO.
Figure 3. Proposed reaction mechanism.
In summary, we have reported a visible-light-promoted direct
oxidative C−H amidation of heteroarenes. Nitrogen-centered
radicals directly generated from sulfonamides were proved to be
the key intermediates. All reactions proceeded at room
temperature under visible light irradiation. Bleach (aqueous
NaClO solution), which is clean and economic, was used as the
solely oxidant. A series of heteroarenes, including indoles,
pyrroles, and benzofurans, could undergo this amidation with
high yields (up to 92%). All the amidated products were isolated
in single regioisomer. Further explorations on the chemistry of
nitrogen-centered radicals are underway in our laboratory.
Keywords: photochemistry • visible light • CH amidation •
nitrogen-centered radical • heterocycle
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Based on these observations, a possible mechanism for this
transformation is proposed. As shown in Figure 3, the
photocatalyst Ir(ppy)2(dtbbpy)PF6 (I) is excited by visible light to
generate excited photocatalyst Ir(ppy)2(dtbbpy)PF6*. It is then
+
oxidatively quenched by NaClO to give Ir(ppy)2(dtbbpy)PF6 . N-
methyl-p-toluenesulfonamide
(2a)
was
oxidized
by
+
Ir(ppy)2(dtbbpy)PF6 with the assistance of base to give NCR
6[14-15] and regenerate Ir(ppy)2(dtbbpy)PF6. Radical 6 adds onto
N-methylindole 1a to afford intermediate 11, which is oxidized,
most likely by NaClO，to form cation intermediate 12. Ultimately,
2-amidated indole 3a is produced after deprotonation.
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Chemistry - A European Journal
10.1002/chem.201604014
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Kun Tong, Xiaodong Liu, Yan Zhang *
and Shouyun Yu *
Page No. – Page No.
Visible-Light-Induced Direct Oxidative
C−H Amidation of Heteroarenes with
Sulfonamides
A direct oxidative C−H amidation of heteroarenes with sulfonamdes via nitrogen-
centered radical under photoredox catalysis has been achieved.
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