Catalytic C-C coupling of diazo compounds with arylboronic acids: Using surface modified sewage sludge as catalyst

Article abstract of DOI:10.1039/d0gc00317d

A green, mild and efficient synthesis of diarylmethines using sewage sludge-derived carbonaceous materials (SW) by perchloric acid catalyzed coupling reactions between diazo compounds and arylboronic acids was developed. The reaction shows a high level of functional tolerance and a broad substrate scope. Furthermore, the highly selective 1,2-alkyl shift products were furnished through the sterically demanding R4, R5 migration of diazo compounds (3-diazochromanone). The structures of 1,2-shift products have been further confirmed by single-crystal X-ray analysis. Significantly, the synthesis of the core structures of darifenacin (a clinical drug for overactive bladder syndrome, OAB) and diclofensine (a stimulant drug showing antidepressant and monoamine reuptake inhibitor activity) further demonstrated the efficacy and synthetic potential of this method. This journal is

Full text of DOI:10.1039/d0gc00317d

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DOI: 10.1039/D0GC00317D
ARTICLE
Catalytic C−C Coupling of Diazo Compounds with Arylboronic
Acids: Using Surface Modified Sewage Sludge as Catalyst
Received 00th January 20xx,
Accepted 00th January 20xx
Zhipeng Zhang1,3, Yang Yu2,4, Yuxing Xie3, Timothy Hughes,4 Jun Xu,5 Fei Huang*3 and He
Huang*,1,3
DOI: 10.1039/x0xx00000x
A green, mild and efficient synthesis of diarylmethines via sewage sludge-derived carbonaceous materials (SW) by
perchloric acid catalyzed coupling reactions between diazo compounds and arylboronic acids was developed. The reaction
shows a high level of functional tolerance and broad substrate scope. Furthermore, the highly selective 1,2-alkyl shift
products were furnishend through the sterically demanding R4, R5 migration of diazo compounds (3-diazochromanone).
The structures of 1,2-shift products have been further confirmed by single-crystal X-ray analysis. Significantly, the systhesis
of the core structures of darifenacin (clinical drug for overactive bladder syndrome, OAB) and diclofensine (stimulant drug
showing antidepressant and monoamine reuptake inhibitor activity) further demonstrated the efficacy and synthetic
potential
of
this
method.
coupling with ArSi(OMe)3 and ArSnMe3 (Scheme 1c).8 These
transformations provide effective methods to afford
diarylacetate derivatives, but developing greener and
sustainable methods for these transformations have always
been a serious challenge. Boronic acid derivatives are stable,
nontoxic, and easily available, becoming popularity within the
synthetic organic chemistry.9 Most recently, an alternative
synthesis of diarylacetates were accomplished via C-C coupling
of diazo compounds with arylboronic acids (Scheme 1d). These
transformations often need transition-metal catalysts,10 such
as Pd10a or Rh10b-d, as well as the strong base (iPr2NH)11 or
other additive12 (CF3TMS6c,12a or NH4Cl12b). With this context,
we wonder whether the cheaper and ubiquitous sewage
sludge-derived carbonaceous materials (SW) could be used as
a greener catalyst for these transformations. This work,
surface modified SW-I will be used as valuable and greener
catalyst for C-C coupling without using additional base or
addictive (Scheme 1e).
Introduction
Diarylacetates1 are ubiquitous subunits which present in
therapeutically important marketed drugs, bioactive molecules
and natural products (Fig. 1). In this area, darifenacin is used
for the treatment of overactive bladder syndrome.2 BPA-COOH
is a bioactive molecule which exhibits antiproliferative activity
against MCF-7 cell lines.3 Bromophenol derivative is one of the
natural products from the red alga, numerous recent studies
have shown that they have anti-inflammatory, anti-oxidative
and anti-tumorigenic activities.4
In view of the medicinal applications, green and highly
efficient synthesis of diarylacetate derivatives has attracted
much attention. Classical syntheses of diarylacetate derivatives
suffer from the use of toxic reagents,5a multi-step reactions5b
and harsh reaction conditions.5c Based on these classic
methods, new synthetic methods have been gradually
developed. Such as transition-metal catalyzed direct arylation
of aryl acetate derivatives6a-b or α-halo aryl acetate
derivatives,6c as well as tandem cross-coupling of ethyl
diazoacetate (EDA) (Scheme 1a).6d Diazo compounds could also
be used for the synthesis of diarylacetate derivatives through
C-H bond functionalization with phenols (Scheme 1b)7 or
OH
OH
Br
OH
Br
H2N
Br
OH
O
OH
O
N
O
O
MeO
HO
OH
darifenacin
BPA-COOH
bromophenol derivative
from the red alga
drug for overactive
bladder syndrome
inhibition for breast
cancer MCF-7 cells
Fig. 1 Diarylacetate group in biologically active compounds.
[1]
[2]
[3]
School of Biology and Biological Engineering, South China University of
Technology, Guangzhou, 510006, China.
School of Environmental Science and Engineering, Nanjing Tech
University, Nanjing, 211816, China.
School of Food Science and Pharmaceutical Engineering, Nanjing Normal
University, Nanjing, 210023, China.
[4]
[5]
Manufacturing, CSIRO, Clayton, Victoria 3169, Australia.
Aba Chemicals Corporation, Shanghai, 200063, China.
These authors contributed equally to this work.
Email: huangfei0208@yeah.net; huang_h@njnu.edu.cn
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ARTICLE
Journal Name
Ar'
Table 1. Screening the optimum conditions for the synthesis of 3aa
ArB(OH)2
+
View Article Online
DOI: 10.1039/D0GC00317D
LG
CO2R
Ar'
Ar
Ar'
[Pd]
[Pd]
(a)
+
Ar
X
CO2R
LG = Cl, Br, I
N2
CO2R
N2
OH
B
Ar
I
X = Cl, Br
conditions
+
O
+
OH
Ar'
I
H
CO2R
EDA
OH
O
O
O
OH
H
1a
2a
3a
OH Ar'
Ar'
CO2R
(C6F5)3B
[Au]
R'
1a:2a
Temp.
(oC)
70
70
70
Yieldb
(%)
trace
19
R'
+
(b)
N2
CO2R
R'
Entry
Catalyst
Solvent
metal-free
(equiv)
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
1:1.5
1:1.6
1:1.7
1:1.4
1:1.6
Ar'
CO2R
Ar'
1
2
3
DCE
DCE
DCE
—
SWc
Ar'
[Rh]
Ar'
[Rh]
(c)
(d)
ArSi(OMe)3
ArB(OH)2
ArSnMe3
+
N2
+ N2
CO2R
c
23
SW-Ⅱ
CO2R
CO2R
Ar
c
4
DCE
70
20
SW-Ⅲ
Transition-metal catalysts
Strong base
c
Ar'
Ar'
5
DCE
70
25
SW-Ⅳ
[Rh], [Pd]
+
+
N2
CO2R
CO2R
c
strong base or other
additive
CO2R
6
SW-Ⅴ
DCE
70
22
Ar
Other additive
c
7
8
9
DCE
DCE
DCE
70
70
70
23
12
56
SW-Ⅵ
greener catalyst
d
HClO4
Waste as valuable catalyst
Greener and reusable
Ar'
Ar'
Ar
SW-I
c
SW-Ⅰ
ArB(OH)2
(e)
N2
This work
CO2R
10
11
12
13
14
15
16
17
18
19
20
21f
DCE
70
59
SW-Ⅰ
Additive-free
e
DCE
70
45
SW-Ⅰ
DMF
Toluene
1,4-dioxane
CH3CN
DCE
70
19
SW-Ⅰ
SW-Ⅰ
SW-Ⅰ
SW-Ⅰ
SW-Ⅰ
SW-Ⅰ
SW-Ⅰ
SW-Ⅰ
SW-Ⅰ
SW-Ⅰ
Scheme 1. Synthesis of diarylacetates.
70
35
70
28
Wastewater is one of the most abundant residues which
derives from industry and domestic activities.13 Sewage sludge
is a major by-product generated in wastewater treatment. The
main contaminants of sewage sludge are proteins,
carbohydrates, heavy metals, pathogenic bacteria and other
inorganic or organic pollutants, presenting a high risk to the
environment.14 So far, traditionally sewage sludge has been
disposed in landfill sites or use as fertilizer.15 On the other
hand, the sewage sludge could be also activated by thermal or
chemical activation methods. The latter method involves the
impregnation of waste sludge with a salt, acid or base.16
Notably, carbonization of sewage sludge under the pyrolysis to
produce sewage sludge-derived carbonaceous materials (SW)
has been a sustainable method for appropriate use of sewage
sludge. Because of its greener, low cost and catalytically active
characteristics, which could be used as adsorbents for air
pollution, organic pollutants and heavy metals.17 Further, it
also could be used as a beneficial catalyst for degradation of
organic wastewater or even for preparation of the surfactants,
microp lastics, sewage sludge biochar (SSBC) and
nanoparticles.18 Currently, Luque groups19 have reported that
sewage sludge material would be also used for the selective
oxidation of isoeugenol to vanillin. We reasonably envisioned
whether SW can be used as advanced and high-activity catalyst
for organic synthesis. In this paper, we reported SW-I
catalyzed C-C coupling reactions of diazo compounds with
arylboronic acids. SW was treated by HClO4, HCl, H2SO4, H3PO4,
HNO3 NaOH respectively, we called them SW-Ⅰ (HClO4), SW-
Ⅱ (HCl), SW-Ⅲ (H2SO4), SW-Ⅳ (H3PO4), SW-Ⅴ (HNO3) and
SW-Ⅵ (NaOH)17, common soil also treated by HClO4, and we
called Soil-Ⅰ (HClO4)17. (see the SI for details).
70
25
60
47
DCE
reflux
70
45
DCE
61
DCE
70
55
DCE
70
51
DCE
70
46
aConditions: 1a (0.5 mmol), 2a, catalyst (50 mg), solvent (5 mL), 0.1 MPa
air, 6 h; symbol “-” means no catalyst. bIsolated yields. 75 mg. dHClO4 (2
c
mg). e25 mg. fSW-I reusing one time, 10 h.
2-phenylacetate 1a and phenylboronic acid 2a were chosen as
the model substrates to optimize the reaction conditions
(Table 1). We found that the reaction did not occur in the
absence of SW catalyst (entry 1), and a variety of SWs (SW–
SW-Ⅴ) produced the C-C coupling product 3a (entries 2-6)
with low yield (less than 25%). We considered that the base
might accelerate the transformation and promote the yield.11
SW-Ⅵ (SW treated by NaOH) was used as a catalyst, reducing
the yield to 23% (entry 7). Besides, using HClO4 as only
catalyst, it also could not give a satisfactory yield (entry 8),
indicating that this reaction was not caused by acid. By
contrast, when SW-Ⅰ (SW treated by HClO4) was used as a
catalyst, the yield could remarkably improve to 56% in DCE at
o
70 C for 6 h (entry 9). It should be noted that the addition of
transition-metal and base were not required—the reactions
proceeded simply by heating both reagents in DCE and SW-Ⅰ.
This promising result encouraged us to screen the other
reaction variables (entries 10-16). When the amount of the
catalyst was reduced to 50 mg, the yield was improved to 59%
(entry 10). However, the yield could not be improved when the
amount of the catalyst was reduced to 25 mg (entry 11).
Further, solvent screen suggested that DCE was optimum for
this transformation (entry 10). The reaction also proceeded at
lower or higher temperature, the conversion was noticeable
decrease (entries 16-17). Moreover, increasing the quantity of
Results and discussion
SW-catalyzed C-C couplings of diazo compounds with
arylboronic acids. At the beginning of this study, ethyl 2-diazo-
2 | J. Name., 2012, 00, 1-3
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ARTICLE
2a (1.6 equiv) could improve the yield to 61% (entry 18), and Scheme 2. Scope of boronic acidsa. aConditions: 1a (0.5 mmol), 2 (0.8
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b
c
DOI: 10.1039/D0GC00317D
further increasing or decreasing the amount of 2a could not mmol), SW-Ⅰ (50 mg), DCE (5 mL), 0.1 MPa air, 6-12 h. Isolated yields. CH3CN
improve yield (entries 19-20). Based on the above results (see as the solvent (5 mL). dGC yield with mesitylene as the internal standard.
the SI for more details: Table S1), the optimum conditions for
this C-C coupling reaction were identified as DCE at 70 oC for 6
h, SW-Ⅰ (50 mg) as catalyst, 1a:2a (equiv) = 1:1.6 (entry 17).
Might because of the diazo compound 1a is so active that it is
easy to form self-coupling product20 or other uncertain by-
products under this catalytic system, only giving the
corresponding product 3a in 61% isolated yield. Further, the
catalyst could be reused and furnish the desired product 3a in
46% yield (entry 21).
With the optimized reaction conditions in hand, we then
inspected the reaction scope of arylboronic acids, summarizing
in Scheme 2. Significantly, the reaction exhibits a high level of
functional group tolerance, affording the desired arylation
products in moderate to good yields. A series of para-
electron-withdrawing substituted groups were compatible,
furnishing the products (3b-d) in good yields (70-83%).
Meanwhile, halide groups (F, Cl, Br and I) were tolerated,
giving the corresponding products (3e-h) in moderate yields
(41-60%). However, the electron-donating groups inhibited the
transformation, furnishing the corresponding products (3i-j) in
low yields (29-43%). Above results suggested that an obvious
electronic effect could influence on the activity of the reaction.
product 3o in good yield (65%). Further, the reaction also
allowed the use of heterocycle-containing pyrimidin-5-
ylboronic acid to furnish heterocycle-aryl esters 3p in good
yields (69%), which might be used as scaffold for drug
discovery.9d,21 Interestingly, CH3CN could be used as the
greener solvent and give the desired products (3c-d) in good
yield (63-70%).
R1
OH
N2
SW-I
B
O
O
R2
+
R1
R2
OH
DCE, 70 oC, air
O
O
Ac
Ac
1
2c
3
CF3
F
Cl
Br
O
O
O
O
O
O
O
, 79%
CH3
O
Ac
Ac
Ac
Ac
c
3s
3t
3u
, 81%
, 78%
3r
,55%
I
OCH3
N
O
O
O
O
O
O
Ac
O
O
O
Ac
Ac
Ac
Ac
d
3v
, 65%
3w
3x
, 72%
, 76%
3y
, 9%
Cl
Moreover,
a
series of meta- and ortho-substituted
Cl
phenylboronic acids were also compatible, affording the
corresponding products (3k–n). Formation of the 3f (56%), 3k
(53%), 3m (35%) and 3j (43%), 3l (41%), 3n (5%, GC yield)
indicated that steric hindrance had an obvious effect on the
transformation of ortho-substituted phenylboronic acids.
Surprisingly, strong sterically hindered naphthalen-2-ylboronic
acid could be well tolerated, giving the
O
O
O
O
O
O
Ac
O
Ac
Ac
3z2
c,e
3z1
, 80%
3z3
, 73%
3z
, 64%
, 85% (72%
)
Cl
O
O
O
O
O
O
O
O
Ac
Ac
Ac
Ac
c
e
3z5
, 75%
3z7
, 72%
3z4
, 61%
3z6
, 80% (62% )
N2
OH
SW-I
DCE, 70 oC, air
O
a
+
a
B
Scheme 3. Scope of diazo compounds . Conditions: 1 (0.5 mmol), 2c (0.8
O
Ar
OH
Ar
O
mmol), SW-Ⅰ (50 mg), DCE (5 mL), 0.1 MPa air, 6 h. bIsolated yields. 12 h. dGC
yield with mesitylene as the internal standard. eCH3CN as the solvent (5 mL)
c
O
3
1a
2
Next, the reactions of various substituted diazo compounds
with (4-acetylphenyl)boronic acid 2c were examined, as
illustrated in Scheme 3. The reaction showed a remarkably
broad scope of applicability with diazo compounds. The
electron-donating or -withdrawing groups at para-positions of
the phenyl ring on R1 were tolerated, affording the
corresponding products (3r-3x) in moderate to good yields (55-
81%). It should be noted that the reaction of 1b, might be
attributed to the strong electron absorption of substituted
group CF3, was sluggish and required 12 h, affording the C-C
coupling product 3r in reduced yield (55%). Besides, might due
to the low selectivity of the nitrogen heterocycles for this
catalytic system, ethyl 2-diazo-2-(pyridin-3-yl) acetate 1i could
only give the product 3y in low GC yield (9%). Ethyl
diazoacetate 1j (EDA) was also tolerated and gave the product
3z in good yield (64%). Meanwhile, methyl 2-diazo-2-
phenylacetate (1k) or chlorine (1l-n) at different positions of
the phenyl ring moiety of 1 could work well and provide the
O
O
O
O
O
O
O
O
F3C
MeO2C
3d
Ac
c
c
3a
3b
, 70%
, 61%
3c
, 83% (70% )
, 71% (63% )
O
O
O
O
O
O
O
O
F
Cl
Br
Cl
I
3e
3f
3g
3h
, 41%
, 59%
, 56%
, 60%
O
O
O
H3C
O
O
O
O
O
H3CO
H3C
3i
3j
, 43%
3k
3l
, 41%
, 29%
, 53%
Cl
CH3
O
O
O
O
N
O
O
O
O
Cl
N
d
3m
3o
3p
, 69%
, 35%
, 65%
3n
, 5%
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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Journal Name
products (3z1-z4) in good to excellent yields (61-85%). Further, affording 1.34 g of the desired product 3z6 in 78%ViiseowlAartteicdle Oynielinlde
other esters such as allyl, benzyl and isobutyl ester variants (Scheme 6). In addition, we envisaged thDeOsIy: n10th.1e0s3i9s/Do0fGtCh0e03c1o7rDe
were also compatible and afforded the products (3z5-z7) in structures of darifenacin (clinical drug for overactive bladder
good yields (72-80%). Fascinatingly, when CH3CN was used as syndrome, OAB)2 and diclofensine (stimulant drug having
the greener solvent, the corresponding product 3z2 and 3z6 antidepressant and monoamine reuptake inhibitor activity).25
were obtained in good yields (72% and 62%).
Synthesis began from the SW-Ⅰ-catalyzed coupling of diazo
Dihydroisoflavone is one of the flavonoids which could compound 1k with phenylboronic acid 2a under the optimized
interfere with different biological processes in human conditions, affording the target product methyl 2,2-diphenylacetate
organism.22 Numerous recent studies have shown that it can 3z8. After several steps of reaction, the core structures of
use clinically for anti-inflammatory, anti-oxidative, anti- darifenacin 5 and diclofensine 6 were obtained, as shown in Fig.2
tumorigenic and reducing the risk of cardiovascular disease (see the SI for more details: Fig. S2).
(anti-diabetic, anti-anxiety, anti-depressant properties).23 With
this context, we expected to synthesize the core structure of
OH
N2
B
SW-I
DCE, 70 oC, 7 h
O
dihydroisoflavone under standard conditions. Interestingly, the
1,2-shift product 4a was obtained without observation of the
expected product 3ct (Scheme 4). Thus, we inferred that the
diazo compound 1t might undergo 1,2-methyl migration to
form 1,2-shift product 4a.24 With this mind, we next evaluated
the 1,2-shift of diazo compounds 1t-1z. As shown in Scheme 5,
the reactions proceeded smoothly under the standard
conditions, efficiently giving the highly selective 1,2-alkyl shift
products (4a-4d) in good to excellent yields (74%-85%).
Interestingly, cycloalkyl could also be migrated, affording the
corresponding products (4e-4g) in good yields (58%-75%).
+
OH
O
O
Ac
O
Ac
1p
, 5 mmol
2c
3z6
, 78%
1.34 g
, 8 mmol
1.31 g
1.26 g
Scheme 6. A gram-scale reaction
SOCl2
Ammonia
H2
N
OH
NH2
O
O
N
O
O
3z8'
5
24% overall yield
darifenacin
NaOH EtOH
Cl
Cl
O
Ph(BOH)2
SW-I
N2
LiAlH4
A
C
dihydroisoflavone
O
O
O
DCE, 70 oC, 6 h
one of the flavonoids
THF (freshly distilled)
0 oC, 0.5 h, rt, 1 h
O
B
O
OH
N
MeO
1k
3z8
6
31% overall yield
diclofensine
O
OH
B
O
O
O
SW-I
DCE, 70 oC, 6 h
Fig. 2 Synthesis of the core structures of darifenacin and
+
HO
N2
O
Ac
O
diclofensine.
Ac
1t
, 0.5 mmol
2c
, 0.8 mmol
4a
, 69%
3ct
, not detected
Mechanistic investigations. A precise reaction mechanism of SW-
Ⅰ-catalyzed C-C coupling reaction is unclear. At the beginning of
the study, the effect of substituents on the phenyl ring of
arylboronic acids was explored, the results are shown in Scheme 7.
The resulting product ratios of 3d and 3l suggested that the
electron-withdrawing group could promote the reaction, while the
electron-donating substituent inhibit the transformation. This also
follows the result that (para-methoxyphenyl) boronic acid 2i afford
the C-C coupling product 3i in lower yield. This might due to that
the electron-withdrawing group could facilitate the coordination of
the electron-rich diazo carbon atom to the electron-deficient boron
center, then, improving the yield.12b
Scheme 4. The synthesis of core structure of dihydroisoflavone.a,b
aConditions: 1t (0.5 mmol), 2c (0.8 mmol), SW-Ⅰ (50 mg), DCE (5 mL), 0.1 MPa
air. bIsolated yields.
R4
R5
O
R4
R5
O
R3
SW-I
R3
DCE, 70 oC, 6 h
N2
O
O
1
4
O
O
O
O
F
Br
Br
O
O
O
O
4a
4e
4b
4c
, 80%
4d
, 74%
, 75%
, 85%
O
O
O
O
1a
(2 mmol)
SW-I
OH
B
OH
B
O
O
O
OH
+
OH
O
4f
4g
, 58%
DCE, 70 oC, 6 h
, 75%
, 69%
MeO2C
MeO
O
X
Scheme 5. 1,2-shift products of chromanone.a,b aConditions: 1 (0.5
mmol), SW-Ⅰ (50 mg), DCE (5 mL), 0.1 MPa air. bIsolated yields.
3d
1.9
3i
: X = OMe
X = CO2Me
2i
1.6 mmol
2d
1.6 mmol
product ratio
:
1
To evaluate the practical utility of the SW-Ⅰ catalyst, a gram- Scheme 7. SW-Ⅰ catalyzed C-C coupling: effect of the substituents.
scale reaction of 1p (1.26 g, 5 mmol) and 2c (1.31 g, 8 mmol) was
carried out with SW-Ⅰ (500 mg) under the optimum conditions,
4 | J. Name., 2012, 00, 1-3
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NMR titration experiments with different acids were cVaierrwieAdrticoleuOt n(Flinige.
It is reported that the C-C coupling reaction depends strongly on
the ease of formation of the zwitterionic intermediate, and the
Lewis acidity of boron is an important factor to form zwitterionic
intermediate.12a Conventional boronic acids, in which two oxygen
atoms decrease the boron Lewis acidity, especially do not couple
with diazo compounds.12a,26 The electron density of boron was
decreased, thereby increasing Lewis acidity of boron.27 Thus, we
speculated whether a certain interaction could decrease the
electron density of boron or reduce the coordination between
hydroxyl groups and boron in boronic acid, thereby increasing the
boron Lewis acidity so as to protonate the diazo compounds and
generate zwitterionic intermediate, finally promoting the C-C
coupling reaction. According to relevant literature reported that the
hydrogen bonding might lead to C-H functionalization and form C-C
bond products.7a We wondered whether the C-C coupling reactions
were related to hydrogen bonding interaction between the hydroxy
group of arylboronic acid and SW-Ⅰ.
1
DOI: 10.1039/D0GC00317D
S5a, S5d-e). It was found that the single hydroxy group
H
resonance of p-tolylboronic acid was shifted upfield when HCl or
HClO4 was added. These results also support that the hydrogen
bond in this catalytic system is caused by SW-Ⅰ and arylbronic acid,
not causing by acid. Furthermore, according to the results of NMR
titration experiments of SW-Ⅰ and acids, we wondered whether
the SW-Ⅰ might act as a Lewis or Brφnsted base. Then, the NMR
titration experiments of different bases were evaluated (Fig. S6).
1
The results showed that the single H resonance of hydroxy group
i
was shifted downfield when Et3N or Pr2NH was added with p-
1
tolylboronic acid. The single H resonance was shifted consistent
with that observed for SW-Ⅰ and in the opposite direction with
acids. The results supported our inference that SW-Ⅰ might act as
a Lewis or Brφnsted base.
a
Table 2. XRF analysis of elements in SW and SW-Ⅰ
Chemical
composition
C
Na2O
MgO
Al2O3
Si2O
SW
SW-I
(Wt%)
12.180
1.016
1.527
15.043
58.201
0.458
1.396
3.815
2.123
1.018
0.720
0.040
0.040
2.308
0.029
0.032
0.011
0.011
0.002
0.021
(Wt%)
13.800
1.154
2.490
15.207
46.269
2.059
1.377
0.166
1.796
9.683
0.618
0.047
0.109
5.050
0.027
0.087
0.009
0.029
0.003
0.021
b
P2O5
SO3
Cl
K2O
CaO
TiO2
Cr2O3
MnO
Fe2O3
CuO
ZnO
Rb2O
SrO
Fig. 3 Properties of SW-Ⅰ. (a, b) SEM and EDS elemental mapping
images.
Y2O3
ZrO2
To gain further mechanistic insight, we should get a better
understanding of SW catalysts. Then, XRF (X-ray fluorescence) and
EDS (Energy Dispersive Spectrometer, noran) were used to analyze
the element content of SW catalysts (Table 2). It is obviously that
the SW-Ⅰ is rich in SiO2 and Al2O3. Apart from C and Cl atoms, the
traditional-metals Fe and Cu (Fe and Cu could be used for metal
carbene insertion reaction),29 as well as Zn, Mn, Mg, Na etc. are also
present. Further, the morphology and structure of SW-Ⅰ catalyst
were observed by SEM (scanning electron microscopy). As shown in
Fig. 3a, it shows roughness surface. EDS mapping images of the
bright dot indicate that C, O, Al, Cl, Fe and Na atoms are
homogeneously distributed within the whole granule of SW-I (Fig.
With this mind, NMR titration experiments were carried out.7a,28
We found that the single 1H resonance of hydroxy group was
shifted downfield and showed a broad singlet when more SW-Ⅰ
was added with p-tolylboronic acid (see the SI for details: Fig. S4a-c).
The broad singlet might be associated with a relatively slow
exchange rate between the free form and that bound to the anion
-
(ClO4 ) p-tolylboronic acid.28 The above results indicated that the
predominant interaction between p-tolylboronic acid and SW-Ⅰ
was hydrogen bonding. Thus, we could infer that C-C coupling
reaction might due to the hydrogen bonding between SW-Ⅰ and
-
3b). The presence of O and Cl atoms prove that anion (ClO4 ) might
hydroxy group of arylbronic acid. Besides, the PH value of SW-Ⅰ present in SW-I, which also consistent that SW-Ⅰ was prepared
with SW treated by HClO4.
Based on the above results, we wondered whether the surface
modification was the main factor due to the activity of SW-Ⅰ,
(SW was surface modified by HClO4) is 6-7 (see the SI for details:
Table S2), indicating that the SW-Ⅰ is not strong acid. To further
demonstrate that the hydrogen bonding is not caused by acids. The
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Journal Name
oC, 6 h. bGC yield with mesitylene as the internal standard. View Article Online
DOI: 10.1039/D0GC00317D
whether this transformation followed the metal carbene process, or
whether this transformation was related to SW-Ⅰ potentially
acting as a Lewis or Brφnsted base. So some control experiments
were carried out, as shown in Table 3. The results showed that in
the presence of a variety of metals could not give the product 3a in
satisfactory yield (entries 1-6). Interestingly, the reaction essentially
did not occur in the presence of transition metals Fe and Cu (Fe and
Cu could be used for metal carbene insertion reaction), indicating
that this transformation might not follow the metal carbene
process (entry 2, entry 4). Even with all the metals added together,
the reaction also could hardly proceed (entry 7). Moreover,
addition of NaClO4 or NaClO4 with other metals (entries 8-9) did not
improve the yields of 3a. These results also suggested that the
elements in SW-I, which might not the main factor for the cause of
the reaction. However, when Soil-I (common soil was surface
modified by HClO4) was used, the yield of 3a was increased (entry
10), but also lower than SW-I (entry 11). Based on the
characterization and comparison of the Soil-I and SW-Ⅰ (Table S4,
Fig. 3 and Fig. S8), we could infer that the surface modification of
SW-I and soil might be the main factor due to the difference
catalytic activity of the two catalysts. Meanwhile, when SW and
HClO4 were directly added together, or just adding HClO4, both
processes could not improve the yield (entry 12, Table 1, entry 8).
The results further indicated the importance of SW surface
modification to the reaction, and also supported that the C-C
coupling reaction was not caused by acid. The NMR titration
experiments suggested that SW-Ⅰ might act as a Lewis or
Brφnsted base. We have screened different bases, the positive
results supported our inference that SW-I might act as a base and
cause the reaction (entries 13-15). This is also consistent with the
articles reported that bases could be used for C-C coupling or
arylation reactions.11,30
Combining the above results, the reaction mechanism was
proposed (Fig. 4).30 Starting with the intermediate A which was
formed by the hydrogen bonding between SW-Ⅰ and arylboronic
acid.28,31 The hydrogen bonding between arylboronic acid and SW-I
might decrease the electron density of boron or reduce the
coordination between hydroxyl groups and boron in arylboronic
acids, thereby increasing the boron Lewis acidity. On the other hand,
since the SW-Ⅰ act as a Lewis or Brφnsted base, it can enhance the
acidity of boron. Then, the boron of intermediate A may have the
proper acidity to form the zwitterionic intermediate B.12a,27,30 The
aryl group on zwitterionic intermediate B was migrated with
releasing molecular nitrogen as the leaving group, giving
intermediate C. Finally, protodeboronation of the intermediate C
would afford the desired C-C coupling product 3,30 releasing SW-Ⅰ
and achieving catalytic cycle.
Ar'
O
Ar
R
O
3
H+
O
O
O
O
Cl
Ar'
H
H
O
O
O
O
O
O
O
O
O
O
B
R
SW
Cl
Cl
Ar
O
O
O
O
Cl
SW
O
O
O
C
OH
B
Ar
OH
N2
Ar
O
B
H
O
Cl
O
O
O
O
H
O
O
O
O
N
Cl
N
O
SW
Ar'
O
H
H
O
O
O
Cl
O
SW
B
R
O
Ar
A
O
O
Cl
N
N
O
O
B
Table 3. Screening of catalytic sites for 3a.a
N2
O
Ar'
R
O
Ar'
R
O
1
O
N2
OH
B
1''
catalysts
O
+
OH
O
DCE, 70 oC, air
O
Fig. 4 Proposed mechanism
O
1a
2a
3a
Entry
Catalyst
Al2O3
FeCl3
FeI2
Wt (mg)
Yieldb(%)
21
NR
14
NR
1
2
3
4
5
6
10
3
3
3
3
Conclusion
In summary, this is the first example of the surface modification
of sewage sludge-derived carbonaceous materials by perchloric acid
as greener catalyst for C-C coupling of diazo compound with
arylboronic acids. Typically, the reactions proceeded under mild
conditions, with good substrate scope, and ease in further
transformations. Moreover, we have also developed a simple
method for preparing the 1,2-shift products of chromanone from 3-
diazochromanone. It should be noted that this work might provide
new avenues to catalyst research and give an alternative strategy
for the selection of catalysts in organic chemistry.
CuCl2
c
MnCl2
10
40
c
ZnCl2
3
Al2O3+FeCl3+FeI2+
MnCl2+ZnCl2+CuCl2
NaClO4
NaClO4+FeCl3
Soil-I
10+3+3+
3+3+3
10
10+3
50
50
50+2
30
7
NR
8
9
11
NR
39
90
8
45
37
51
10
11
12
13
14
15
SW-I
SW+HClO4
K3PO4
Et3N
5
5
Experimental
Preparation of SW catalysts.
iPr2NH
aConditions: 1a (0.5 mmol), 2a (0.8 mmol), DCE (5 mL), 0.1 MPa air,70
6 | J. Name., 2012, 00, 1-3
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ARTICLE
o
The surface of SW was modified by different kinds of acids or bases chromatography with petroleum ether (60-90 C)/AcOEt (10:1) to
View Article Online
to gain SW catalysts. SW was prepared by using municipal sewage afford the corresponding 4a as a white solidD(O65I: 1m0g.1,07359%/D)0.GC00317D
sludge from wastewater treatment plant (WWTP) in China. Sewage Data availability. The X-ray crystallographic structures for
sludge was dried to constant weight at 105 °C and carbonized at 600 °C compounds 4b reported in this article have been deposited at the
for 4 h under a heating rate of 3 °C min−1 and a high purity nitrogen Cambridge Crystallographic Data Centre (CCDC), CCDC 1975819 for
(99.999 wt%) flow of 500 mL min−1. After the furnace had cooled to 4b. (http://www.ccdc.cam.ac.uk/data_request/cif). The authors
room temperature, SW was obtained. Different kinds of acids or declare that all other relevant data supporting the findings of this
bases were used to treat the SW. In the acid or base treatment study are available within the article and its Supplementary
process, 50 mL of SW were produced by immersing carbonized SW Information files.
with the same volume of HClO4 (35.4 wt%), HCl (20.5 wt%), H2SO4
(63.4 wt%), H3PO4 (45.4 wt%), HNO3 (40.5 wt%) and NaOH (39.5 wt%)
for 24 h for 24 h, respectively. Then, SW-Ⅰ (HClO4), SW-Ⅱ (HCl),
Conflicts of interest
SW-Ⅲ (H2SO4), SW-Ⅳ (H3PO4), SW-Ⅴ (HNO3) and SW-Ⅵ (NaOH)
were washed with deionized water until the pH of the washing water
reached 6-7 and the recovered solids were dried at room
temperature. Soil-Ⅰ (common soil treated by HClO4) was prepared
by the same method of SW-Ⅰ.
There are no conflicts to declare.
Acknowledgements
We are grateful to National Natural Science Foundation of
China (21901124), Natural Science Foundation of the Jiangsu
Higher Education Institutions of China (19KJB150032,
19KJB610013), China Postdoctoral Science Foundation
(2019M651809) and Jiangsu Planned Projects for Postdoctoral
Research Funds (2019K110) for support of this research.
Catalyst characterization.
X-ray Fluorescence (XRF, Magix 601) and Energy Dispersive
Spectrometer (EDS, noran) were used to analyse the element
content in the SW catalysts. The morphology and microstructure of
SW-Ⅰ catalyst were examined by scanning electron microscope
(SEM, HITACHI S4800) and transmission electron microscopy (TEM,
JSM7500F).
General experimental procedures.
References
A typical procedure for the synthesis of α-diazoesters24b,32 (1) 
Synthesis of 1a: DBU (2.24 mL, 15 mmol) was added slowly to a
stirred solution of ethyl 2-phenylacetate (sm1a 1.59 mL, 10.0 mmol)
and tosylazide (sm2, 2.42 mL, 11.0 mmol) in the CH3CN (20 mL) at 0
oC. Then, it was placed in microwave reactor that was heated to
40 °C (400 W, monitored by IR temperature sensor) and maintained
at this temperature for 30-40 min. After cooling to room
temperature, the reaction mixture was quenched with saturated
aqueous solution of NH4Cl (5 mL), extracted with CH2Cl2 (3 × 30 mL),
washed with brine (3 × 30 mL), dried over anhydrous Na2SO4, and
concentrated under reduced pressure to give the product. The
residue was purified by flash chromatography (petroleum ether (60-
90 oC)/AcOEt, 10:1) to afford the corresponding ethyl-2-diazo-2-
phenylacetate 1a as a yellow liquid (1.65 g, 87%).
A typical C-C coupling reaction procedure (3). Synthesis of 3a: A
mixture of SW-Ⅰ (50 mg), Phenylboronic acid (2a, 98 mg, 0.8 mmol)
and ethyl 2-diazo-2-phenylacetate (1a, 95 mg, 0.5 mmol) in DCE (5
mL) was stirred at room temperature under 0.1 Mpa air for 1 h,
then the resulting mixture was stirred at 70 oC for 6 h. After
filtrating, the filtrate was dissolved in DCM (20 mL). The DCM
layer was washed with water (3 × 20 mL) and brine (3 × 20 mL).
Then, the organic layer was dried over anhydrous Na2SO4 and
concentrated to get the crude product. The crude product was
purified by flash chromatography with petroleum ether (60-90
oC)/AcOEt (10:1) to afford the corresponding 3a as a colorless liquid
(73 mg, 61%).
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A typical procedure for 1,2-shift products of chromanone (4).
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Green Chemistry
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Journal Name
ARTICLE
View Article Online
DOI: 10.1039/D0GC00317D
ArB(OH)2
up to 85% yield
32 examples
R4
R5
R1
O
O
N2
SW-I
R3
SW-I
R'
O
R2
R
Ar
DCE, 70 oC, air
DCE, 70 oC, air
O
O
high functional
group tolerance
R4, R5 migration
reactions
C-C coupling
reactions
Cl
Cl
or
H2N
O
O
N
N
MeO
Me
4b
darifenacin
diclofensine
crystal structure of
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
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