Visible Light-Induced Decarboxylative Acylarylation of Phenyl Propiolates with α-Oxocarboxylic Acids to Coumarins Catalyzed by Hypervalent Iodine Reagents under Transition Metal-Free Conditions

Article abstract of DOI:10.1002/adsc.201600721

No Abstract. (Figure presented.).

Full text of DOI:10.1002/adsc.201600721

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DOI: 10.1002/adsc.201600721
Visible Light-Induced Decarboxylative Acylarylation of Phenyl
Propiolates with a-Oxocarboxylic Acids to Coumarins Catalyzed
by Hypervalent Iodine Reagents under Transition Metal-Free
Conditions
Shuai Yang,a Hui Tan,a Wangqin Ji,a Xiangbiao Zhang,b,* Pinhua Li,a
and Lei Wanga,c,*
a
Department of Chemistry, Huaibei Normal University, Huaibei, Anhui 235000, Peopleꢀs Republic of China
Fax : (+86)-561-309-0518; phone: (+86)-561-380-2069; e-mail: leiwang@chnu.edu.cn
Department of Chemical Engineering, Anhui University of Science and Technology, Huainan, Anhui 232001, Peopleꢀs
b
Republic of China
E-mail: xbzhang_theochem@yahoo.com
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai 200032, Peopleꢀs
c
Republic of China
Received: July 7, 2016; Revised: October 29, 2016; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201600721.
Introduction
Coumarin and its derivatives are one of the impor-
tant organic molecules with remarkable biological
Ciamician, a pioneering chemist, published a perspec- and medicinal activities. They are widely used as anti-
tive of applying sunlight as a unique natural resource cancer, anti-HIV, antipsoriasis, anti-inflammatory, an-
for chemical transformations in 1912.[1] Since then, tidepressant and antidiabetic drugs.[9] Owing to their
the developments achieved for the organic photo- unique properties, the preparation of coumarins has
chemistry are focused on the use of ultra-violet received considerable attention in the last decades
light.[2] In 2008, MacMillan disclosed the first applica- and a number of the synthetic routes have been de-
tion of the visible light-induced direct asymmetric al- veloped.[10] As one of the classic methods, the Pech-
kylation of aldehydes by merging photoredox cataly- mann condensation is one of the most effective strat-
sis with organocatalysis.[3] As a safe, abundant and re- egies.[11] It is important to note that the transition
newable energy source, visible light-irridiated photo- metal-catalyzed preparation of coumarin derivatives
redox catalysis has received much more attention has emerged as one of the most attractive research
through the unique single electron transfer (SET) areas since a diversity of organic reactions was ach-
pathway (oxidative quenching and reductive quench- ieved in the presence of Pd as an effective catalyst.[12]
ing cycles) under remarkably mild reaction conditions For example, Trost and Toste developed a Pd-cata-
recently.[4] A number of carbon-carbon and carbon- lyzed addition of propargylic esters to activated phe-
heteroatom bond formations induced by visible light nols, providing functionalized coumarins,[13] Shi and
and Ru, Ir, Cu, Ni complexes,[5] or organic dyes (eosin He described an Au-catalyzed intermolecular addition
Y, fluorescein, rose bengal, and acridinium salts)[6] as of arenes to alkynes or aryl alkynoates for the genera-
photoredox catalysts have been developed, and this tion of coumarins in the presence of AgOTf.[14] More
has become one of the most active research fields in recently, Alper reported a practical preparation of
organic synthesis. On the other hand, hypervalent substituted coumarins through Pd-catalyzed oxidative
iodine reagent (HIR)-catalyzed organic transforma- cyclocarbonylation of 2-vinylphenols with carbon
tions under visible light irradiation in the absence of monoxide (CO).[15] Meanwhile, a Ru-catalyzed decar-
photoredox catalyst for saving the precious metal boxylative annulation of internal alkynes with a-keto
(such as Ru and Ir), or organic dyes were reported.[7] acids for the synthesis of 2,3-disubstituted coumarins
Most recently, Li described a simple, metal- and oxi- was reported.[16] Moreover, other transition metals,
dant-free photochemical strategy for the direct tri- such as Pt-, Rh-, Cu-, Mn-, and Ag-catalyzed synthetic
fluoromethylation of arenes and heteroarenes under methods for the construction of coumarins were also
visible-light irradiation, representing a further direc- developed.[17] It is obvious that the above protocols
tion of photochemistry.[8]
suffer from the drawbacks of toxic heavy metals and
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ligands used in the reactions. In 2015, Wu and co- LED (450–455 nm) was the best light source for the
worker developed an efficient metal-free tandem acy- reaction, and a comparable result was obtained using
lation/cyclization of alkynoates with aldehydes for the sunlight irradiation. However, green LED, red LED,
synthesis of 3-acyl-4-arylcoumarins.[18] It is highly de- purple LED and white light were no longer efficient
sirable to explore more straightforward methods for energy pools for initiating the reaction (Table 1, en-
the synthesis of coumarins under transition metal-free tries 14–18). The solvent screening indicated that the
conditions in organic synthesis and the pharmaceuti- solvent choice was crucial for this reaction. When the
cal industry. On the basis of this understanding and reaction was carried out in benzene, the desired prod-
our early works,[19] herein, we report an efficient hy- uct 3a was obtained in 63% yield (Table 1, entry 19).
pervalent iodine reagent (HIR)-catalyzed decarboxy- No reaction was observed using EtOAc, DCE, THF,
lative carbonylarylation of phenyl propiolates with a- MeCN, DMSO, acetone or Et3N as reaction medium
oxocarboxylic acids under visible-light photolysis in (Table 1, entries 19–26). In the absence of visible
the absence of a photoredox catalyst. The reactions light, no desired product was generated, indicating
generated the corresponding 3-acyl-4-arylcoumarins that visible light is essential in the reaction (Table 1,
in good yields at room temperature under transition entries 27 and 28). Further investigation of BI-OH
metal-free conditions (Scheme 1).
and KPF6 loading, the ratio of 1a to 2a, as well as the
reaction time showed that the optimal reaction condi-
tions were 1a (0.20 mmol), 2a (0.40 mmol), BI-OH
(20 mol%), KPF6 (1.0 equiv.) in toluene (1.0 mL) and
an air atmosphere under 1.5W blue LED irradiation
at room temperature for 24 h.
With the optimized conditions in our hand, the gen-
erality of the decarboxylative acylarylation was ex-
plored. The results are listed in Table 2. Firstly, a vari-
ety of aryl 3-phenylpropiolates (1) in reactions with 2-
oxo-2-phenylacetic acid (2a) were examined, indicat-
ing a broad tolerance of substituted groups on the ar-
omatic rings of 1. Aryl 3-phenylpropiolates with an
electron-donating group, such as Me, Et, i-Pr, or t-Bu
on the para-position of the aromatic rings reacted
with 2a to generate the corresponding products (3b–
e) in 66–81% yields. The reaction of aryl 3-phenylpro-
Scheme 1. Visible light irradiated synthesis of coumarins.
Results and Discussion
For optimization of the reaction conditions, a model piolate with 3,5-(Me)2 on the aromatic ring with 2a af-
reaction of phenyl 3-phenylpropiolate (1a) and 2-oxo- forded the desired product 3f in 74% yield. Mean-
2-phenylacetic acid (2a) was chosen. Firstly, when the while, aryl 3-phenylpropiolates bearing an electron-
model reaction was carried out in the presence of withdrawing group including F, Cl, Br, or I on the
eosin Y (2.0 mol%) or [Ru(bpy)3]Cl2 (2.0 mol%) as para-position of the benzene rings underwent the re-
photoredox catalyst, toluene as solvent at room tem- action to afford the anticipated products 3g–j in 55–
perature under blue LED irradiation for 24 h, no 65% yields. When naphthalen-2-yl 3-phenylpropiolate
product was observed and starting materials were re- was used to react with 2a, the product 3k was ob-
covered (Table 1, entries 1 and 2). To our delight, the tained in 70% yield. It should be noted that a decar-
desired coumarin (3a) was isolated in 28% yield on boxylative acylarylation of phenyl 3-(4-butylphenyl)-
using PhI(OAc)2 (20 mol%) instead of eosin Y or propiolate with 2a proceeded well, leading to product
[Ru(bpy)3]Cl2 (Table 1, entry 3). Other hypervalent 3l in 65% yield.
iodine reagents, such as BI-OH [1-hydroxy-1,2-ben-
On the other hand, the scope of a-oxocarboxylic
ziodoxol-3(1H)-one, BI=1,2-benziodoxol-3(1H)-one], acids (2) was surveyed, shown in Table 3. In general,
ꢀ
BI-OAc and BI-C CPh were examined, and BI-OH 2-oxo-2-arylacetic acids with either electron-sufficient
was found to be the best choice (Table 1, entries 3–6). or electron-deficient groups on the phenyl rings of 2
For further improvement of the reaction efficiency, could react with 3-phenyl phenylpropiolate (1a) and
some additives were added to the reaction system. 3-phenyl (4-methylphenyl)propiolate (1b) to give the
The results indicated that KPF6 was the most effective corresponding products 3m–ab in moderate to good
one among the examined additives (Table 1, entry 7). yields. The reactions of 2-oxo-2-(substituted phenyl)-
Other additives, C6H5SO3Na and (NH4)2C2O4 exhibit- acetic acids with an electron-rich group, such as
ed less efficiency. However, addition of K2CO3, methyl, ethyl, n-butyl or tert-butyl group on the para-
Na2CO3, TsOH and PivOH prohibited the reaction position of the benzene rings led to the desired prod-
completely (Table 1, entries 8–13). The light source ucts (3m–p) in 62–71% yields. Moreover, 2-oxo-2-
also plays an important role in the reaction. Blue (substituted phenyl)acetic acids possessing an elec-
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Table 1. Optimization of the reaction conditions.[a]
Entry
Light
Catalyst
Additive
Solvent
Yield [%][b]
1[c]
2
3
4
5
6
7
8
9
10
11
12
13
14[d]
15[e]
16[f]
17[g]
18
19
20
21
22
23
24
25
26
27[h]
28[i]
blue LED
blue LED
blue LED
blue LED
Blue LED
blue LED
blue LED
blue LED
blue LED
blue LED
blue LED
blue LED
blue LED
green LED
red LED
purple LED
white LED
sunlight
blue LED
blue LED
blue LED
blue LED
blue LED
Blue LED
blue LED
blue LED
–
eosin Y
–
–
–
–
–
–
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
benzene
EtOAc
DCE
N.R.
N.R.
28
24
17
39
48
59
74
N.R.
N.R.
N.R.
N.R.
0
0
0
0
66
[Ru(bpy)3]Cl2
PhI(OAc)2
BI-OAc
ꢀ
BI-C CPh
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
BI-OH
C6H5SO3Na
(NH4)2C2O4
KPF6
K2CO3
Na2CO3
TsOH
PivOH
KPF6
KPF6
KPF6
KPF6
KPF6
KPF6
KPF6
KPF6
KPF6
KPF6
KPF6
KPF6
KPF6
KPF6
KPF6
63
N.R.
N.R.
N.R.
N.R.
N.R.
N.R.
N.R.
0
THF
MeCN
DMSO
acetone
Et3N
toluene
toluene
–
trace
[a]
Reaction conditions: phenyl 3-phenylpropiolate (1a, 0.20 mmol), 2-oxo-2-phenylacetic acid (2a, 0.40 mmol), photoredox
catalyst (2.0 mol%) or HIR catalyst (20 mol%), additive (1.0 equiv.), solvent (1.0 mL) at room temperature under light ir-
radiation in air for 24 h.
[b]
[c]
[d]
[e]
[f]
Isolated yield, N.R.=no reaction.
Blue LED (450–455 nm, 1.5 W).
Green LED (530–535 nm, 1.5 W).
Red LED (695–700 nm, 1.5 W).
Purple LED (400–405 nm, 1.5 W).
White LED (8 W).
[g]
[h]
[i]
In the dark.
At 808C in dark. HIR=hypervalent iodine reagent.
tron-poor group, such as fluoro, chloro, bromo, or (ortho-chlorophenyl)acetic acid, 2-oxo-2-(ortho,meta-
iodo group on the para-position of the benzene rings dichlorophenyl)acetic acid, 2-oxo-2-(ortho,meta-dime-
afforded the corresponding products 3q–t in 55–67% thylphenyl)acetic acid were carried out under the op-
yields. 2-Oxo-2-(substituted phenyl)acetic acids with timal reaction conditions, providing the desired prod-
a methyl or bromo group on the meta-position of the ucts 3v (51% yield), 3w (57% yield), 3z (57% yield),
phenyl ring delivered the products 3x and 3y in 58% and 3ab (61% yield). It is noteworthy that 2-(naph-
and 69% yields, respectively. A slight steric effect was thalen-1-yl)-2-oxoacetic acid reacted with 3-phenyl (4-
observed when the reactions of 1a with a methyl or ethylphenyl)propiolate to generate the product 3u in
chloro group on the ortho-position of phenyl ring in 67% yield. In addition, the reaction of 2-oxo-2-(para-
2-oxo-2-(substituted phenyl)acetic acids including 2- chlorophenyl)acetic acid with 3-phenyl (4-methylphe-
oxo-2-(ortho-methylphenyl)acetic
acid,
2-oxo-2- nyl)propiolate afforded the corresponding decarboxy-
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Table 2. The scope of aryl 3-arylpropiolates (1).[a,b]
[a]
Reaction conditions: aryl 3-arylpropiolate (1, 0.20 mmol), 2-oxo-2-phenylacetic acid (2a, 0.40 mmol), BI-OH
(20 mol%), KPF6 (1.0 equiv.) in toluene (1.0 mL) at room temperature under blue LED (450–455 nm, 1.5 W) irra-
diation in air for 24 h.
Isolated yields.
[b]
lative acylarylation product 3aa in 66% yield. Howev- present conditions (Scheme 2d), demonstrating a key
er, the reactions of 2-oxo-2-(thiophen-2-yl)acetic acid step of the addition of the formed benzoyl radical to
with 3-phenyl phenylpropiolate (1a), 2-(furan-2-yl)-2- 1a.
oxoacetic acid with 1a, and pyridin-4-yl 3-phenylpro-
In order to further explore the reaction mechanism,
piolate with 2-oxo-2-phenylacetic acid (2a) under the an important intermediate I was prepared in high
present reaction conditions, but failed. In addition, yield
according
to
the
reported
method
the reactions 2-oxo-2-aliphatic acetic acids, such as 2- (Scheme 2e),[20] which underwent the reaction with 1a
oxopropanoic acid and 2-oxo-3-phenylpropanoic acid to afford the anticipated product 3a in 76% yield
with 1a did not occur under the recommended reac- (Scheme 2f). Meanwhile, the reaction of prepared I
tion conditions because of the lower stability of ali- with 1a was performed without light irradiation at
phatic acyl radicals than aromatic ones.
When 2,2,6,6-tetramethyl-1-piperidinyloxy that I may be involved as an important intermediate
(TEMPO) or 2,6-di-tert-butyl-4-methylphenol (BHT), in the reaction.
958C, providing 3a in 14% yield. These results imply
a radical scavenger, was added to the model reaction
On the basis of above results and the reported in-
of 1a with 2a, the decarboxylative acylarylation was vestigation,[17] a possible mechanism for the photore-
completely inhibited (Scheme 2a). As 2-oxo-2-phenyl- action of 1a and 2a is proposed, and shown in
acetic acid (2a) was carried out in the presence of Scheme 3. Firstly, 2-oxo-2-phenylacetic acid (2a)
TEMPO or BHT without 1a, the corresponding reacts with BI-OH to generate intermediate I,[20]
adduct 4[7b] (shown in Scheme 3) or 5 was isolated in which undergoes a homolytic cleavage of the I O
À
83% and 38% yields, respectively, implying the for- bond under blue LED irradiation to form iodanyl
mation of a benzoyl free radical during the reaction radical II,[7a,21] and benzoyl radical III along with the
(Scheme 2b). On the other hand, when 1a was treated generation of CO2, which was detected by FT-IR
in the absence of 2a, no product 6 was obtained analysis of the resulting gas (Supporting Information).
(Scheme 2c). In addition 2a, on reaction with the pre- The formed III reacts with 1a via a free radical addi-
ꢀ
pared 6, could not be transformed into 3a under the tion to the C C bond of 1a, and is followed by an in-
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Table 3. The scope of a-oxocarboxylic acids (2).[a,b]
[a]
Reaction conditions: aryl 3-arylpropiolate (1, 0.20 mmol), 2-oxo-2-phenylacetic acid (2a, 0.40 mmol), BI-OH
(20 mol%), KPF6 (1.0 equiv.) in toluene (1.0 mL) at room temperature under blue LED (450–455 nm, 1.5 W) irradia-
tion in air for 24 h.
Isolated yields.
[b]
tramolecular radical cyclization to afford intermediate under metal-free conditions. Further applications of
IV, which undergoes a dehydrogenative aromatiza- this protocol and investigations on the detailed reac-
tion, providing product 3a and BI-H. The obtained tion mechanism are underway in our laboratory.
BI-H reacts with 2a to give I for the next run, along
with the generation of H2, which was detected by GC
analysis (Supporting Information). It should be noted
that free radical II generated in situ from I was
trapped by BHT, providing the desired product 5 in
27% yield and 7 (HR-MS analysis, Supporting Infor-
mation).[7b,22]
Experimental Section
General Considerations
All 1H NMR and 13C NMR spectra were recorded on
a 400 MHz Bruker FT-NMR spectrometer (400 MHz or
100 MHz, respectively). All chemical shifts are given as d
values (ppm) with reference to tetramethylsilane (TMS) as
an internal standard. The peak patterns are indicated as fol-
lows: s, singlet; d, doublet; t, triplet; m, multiplet; q, quartet.
The coupling constants, J, are reported in Hertz (Hz). High
resolution mass spectroscopy data of the product were col-
lected on an Agilent Technologies 6540 UHD Accurate-
Mass Q-TOF LC/MS (ESI).
a-Oxocarboxylic acids and phenyl 3-phenylpropiolate are
prepared according to reported methods.[23] The chemicals
and solvents were purchased from commercial suppliers –
either Aldrich (USA), or Shanghai Chemical Company (P.
R. China). All the solvents were dried and freshly distilled
in N2 prior to use. Products were purified by flash chroma-
Conclusions
In conclusion, we have developed an efficient and
visible light-initiated, hypervalent iodine reagent-cata-
lyzed decarboxylative acylarylation of phenyl propio-
lates with a-oxocarboxylic acids, providing a novel
and direct approach to 3-acylated coumarins. The re-
action was based on a BI-OH-catalyzed process and
was irradiated by blue LED in the absence of any
photoredox catalyst. The reactions generated the cor-
responding products in good yields through a tandem
decarboxylative radical addition/cyclization reaction tography on 200–300 mesh silica gels, SiO2.
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Typical Procedure for the Decarboxylative
Acylarylation of Phenyl 3-Phenylpropiolate with a-
Oxocarboxylic Acids
A 5-mL oven-dried reaction vessel equipped with a magnetic
stirrer bar was charged with phenyl 3-phenylpropiolate (1a,
44.4 mg, 0.20 mmol), 2-oxo-2-phenylacetic acid (2a, 60.0 mg,
0.40 mmol), BI-OH (10.6 mg, 0.040 mmol), KPF6 (36.8 mg,
0.20 mmol) and toluene (1.0 mL). The reaction vessel was
exposed to blue LED (450–455 nm, 1.5 W) irradiation at
room temperature in air with stirring for 24 h. After comple-
tion of the reaction, the mixture was concentrated to yield
the crude product, which was further purified by flash chro-
matography (silica gel, petroleum ether/ethyl acetate=7:1
to 10:1) to give the desired product 3a; yielkd: 48.3 mg
(74%).
Characterization Data for the Products
3a:[10k] 1H NMR (400 MHz, CDCl3): d=7.80 (d, J=7.6 Hz,
2H), 7.64–7.60 (m, 1H), 7.52–7.46 (m, 2H), 7.38–7.26 (m,
9H); 13C NMR (100 MHz, CDCl3): d=192.12, 158.77,
153.74, 152.94, 136.25, 133.81, 132.71, 132.32, 129.49, 129.23,
128.71, 128.58, 128.56, 127.97, 126.02, 124.67, 119.45, 117.17.
3b:[10k] 1H NMR (400 MHz, CDCl3): d=7.80 (d, J=
7.6 Hz, 2H), 7.52–7.48 (m, 1H), 7.38–7.32 (m, 5H), 7.27–
7.26 (m, 3H), 7.18–7.16 (m, 1H), 7.08–7.06 (m, 1H), 2.50 (s,
3H); 13C NMR (100 MHz, CDCl3): d=192.32, 159.00,
153.86, 153.09, 144.22, 136.42, 133.68, 132.56, 129.38, 129.24,
128.69, 128.53, 128.49, 127.66, 125.86, 124.89, 117.30, 117.02,
21.70.
Scheme 2. Control experiments.
3c: 1H NMR (400 MHz, CDCl3): d=7.80 (d, J=7.6 Hz,
2H), 7.52–7.48 (m, 1H), 7.38–7.33 (m, 5H), 7.30 (s, 1H),
7.27–7.26 (m, 2H), 7.21–7.19 (m, 1H), 7.11–7.09 (m, 1H),
2.79 (q, J=7.6 Hz, 2H), 1.31 (t, J=7.6 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=192.31, 159.03, 154.00, 153.09, 150.45,
136.44, 133.67, 132.59, 129.36, 129.23, 128.69, 128.52, 128.48,
127.79, 124.93, 124.68, 117.20, 116.11, 28.92, 15.03; HR-MS
(ESI): m/z=355.1325 ([M+H]+), calcd. for C24H18O3:
355.1329.
3d: 1H NMR (400 MHz, CDCl3): d=7.80 (d, J=7.6 Hz,
2H), 7.49 (t, J=7.2 Hz, 1H), 7.37–7.32 (m, 6H), 7.28–7.25
Scheme 3. Possible reaction mechanism.
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(100 MHz, CDCl3): d=191.69, 158.06, 153.86, 152.37, 136.08,
133.92, 131.90, 129.71, 129.21, 128.95, 128.70, 128.62, 128.10,
126.83, 126.13, 120.38, 118.51.
(m, 2H), 7.23–7.21 (m, 1H), 7.15–7.12 (m, 1H), 3.09–2.99
(m, 1H), 1.32 (d, J=6.8 Hz, 6H); 13C NMR (100 MHz,
CDCl3): d=192.35, 159.08, 155.12, 154.03, 153.10, 136.44,
133.69, 132.58, 129.39, 129.23, 128.69, 128.53, 128.49, 127.87,
124.92, 123.38, 117.31, 114.74, 34.26, 23.58; HR-MS (ESI):
m/z=369.1483 ([M+H]+), calcd. for C25H20O3: 369.1485
3i:[10k] 1H NMR (400 MHz, CDCl3): d=7.80–7.78 (m, 2H)
7.53–7.49 (m, 2H), 7.39–7.34 (m, 5H), 7.26–7.23 (m, 4H);
13C NMR (100 MHz, CDCl3): d=191.70, 158.14, 153.95,
152.32, 138.78, 136.11, 133.91, 131.96, 129.70, 129.22, 128.86,
128.69, 128.61, 125.91, 125.24, 118.13, 117.42.
3e:[10k] 1H NMR (400 MHz, CDCl3): d=7.80 (d, J=7.2 Hz,
2H), 7.52–7.48 (m, 2H), 7.38–7.31 (m, 5H), 7.29–7.22 (m,
4H), 1.39 (s, 9H); 13C NMR (100 MHz, CDCl3): d=192.30,
159.10, 157.46, 153.83, 152.95, 136.45, 133.67, 132.56, 129.38,
129.22, 128.68, 128.52, 128.48, 127.52, 125.06, 122.20, 116.92,
113.96, 35.33, 30.99; HR-MS (ESI): m/z=383.1642 ([M+
H]+), calcd. for C26H22O3: 383.1642.
3j: 1H NMR (400 MHz, CDCl3): d=7.79 (d, J=7.2 Hz,
2H) 7.53–7.50 (m, 1H), 7.39–7.33 (m, 5H), 7.31–7.24 (m,
3H), 7.21–7.18 (m, 1H), 7.02–6.97 (m, 1H); 13C NMR
(100 MHz, CDCl3): d=191.77, 164.95 (d, J=254.5 Hz),
158.40, 155.00, 154.87, 152.55 (d, J=1.2 Hz), 136.21, 133.84,
132.19, 129.82 (d, J=10.2 Hz), 129.64, 129.22, 128.63 (d, J=
7.0 Hz), 128.61, 124.91 (d, J=3.0 Hz), 116.24 (d, J=2.9 Hz),
112.77 (d, J=22.4 Hz), 104.69 (d, J=25.5 Hz); HR-MS
(ESI): m/z=345.0920 ([M+H]+), calcd. for C22H13FO3:
345.0921.
3f: 1H NMR (400 MHz, CDCl3): d=7.80 (d, J=7.6 Hz,
2H), 7.50 (t, J=7.6 Hz, 1H), 7.38–7.32 (m, 5H), 7.30 (s,
1H), 7.26–7.24 (m, 2H), 6.87 (s, 1H), 2.52 (s, 3H), 2.29 (s,
3H); 13C NMR (100 MHz, CDCl3): d=192.43, 159.02,
153.26, 150.28, 136.41, 135.16, 133.74, 133.66, 132.79, 129.24,
128.72, 128.50, 128.42, 126.31, 125.68, 125.30, 118.95, 20.83,
15.57; HR-MS (ESI): m/z= 355.1335 ([M+H]+), calcd. for
C24H18O3: 355.1329.
3k: 1H NMR (400 MHz, CDCl3): d=8.69–8.66 (m, 1H),
7.92–7.88 (m, 1H), 7.85–7.83 (m, 2H), 7.73–7.69 (m, 2H),
7.64 (d, J=8.8 Hz, 1H), 7.54–7.50 (m, 1H), 7.40–7.36 (m,
5H), 7.33–7.30 (m, 2H), 7.27–7.25 (m, 1H); 13C NMR
(100 MHz, CDCl3): d=192.26, 158,76, 154,01, 151,29, 136.42,
135.18, 133.74, 132.81, 129.42, 129.35, 129.29, 128,75, 128.57,
127.77, 127.48, 125,40, 124.41, 123.09, 122.85, 122.76, 114.67;
HR-MS (ESI): m/z=377.1172 ([M+H]+), calcd. for
C26H16O3: 377.1172.
3g: 1H NMR (400 MHz, CDCl3): d=7.86–7.78 (m, 3H),
7.60–7.50 (m, 2H), 7.40–7.24 (m, 5H), 7.25–7.24 (m, 2H),
7.00–6.98 (m, 1H); 13C NMR (100 MHz, CDCl3): d=191.72,
157.94, 153.48, 152.46, 136.08, 133.95, 133.91, 131.85, 129.69,
129.20, 128.82, 128.69, 128.62, 126.43, 126.28, 119.03, 98.55;
HR-MS (ESI); m/z=452.9986 ([M+H]+), calcd. for
C22H13IO3: 452.9982.
3l: 1H NMR (400 MHz, CDCl3): d=7.79 (d, J=7.6 Hz,
2H), 7.63–7.59 (m, 1H), 7.51–7.45 (m, 2H), 7.37–7.33 (m,
3H), 7.28–7.24 (m, 1H), 7.18–7.11 (m, 4H), 2.58–2.54 (m,
2H), 1.58–1.50 (m, 2H), 1.32–1.22 (m, 2H), 0.90 (t, J=
3h:[10k] 1H NMR (400 MHz, CDCl3): d=7.78 (d, J=
8.0 Hz, 2H) 7.65 (s, 1H), 7.53–7.49 (m, 1H), 7.39–7.34 (m,
6H), 7.26–7.23 (m, 2H), 7.15 (d, J=8.4 Hz, 1H); 13C NMR
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7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=192.26,
158.79, 153.78, 153.12, 144.52, 136.38, 133.60, 132.55, 129.56,
129.22, 128.71, 128.55, 128.47, 128.05, 125.86, 124.53, 119.53,
117.13.35.31, 33.10, 22.15, 13.85; HR-MS (ESI): m/z=
383.1645 ([M+H]+), calcd. for C26H22O3: 383.1642.
125.59, 124.56, 119.59, 177.15, 35.17, 30.98: HR-MS (ESI):
m/z=383.1637 ([M+H]+), calcd. for C26H22O3: 383.1642.
3q: 1H NMR (400 MHz, CDCl3): d=7.74 (d, J=8.4 Hz,
2H), 7.66–7.61 (m, 1H), 7.52–7.47 (m, 3H), 7.38–7.34 (m,
3H), 7.31–7.25 (m, 4H); 13C NMR (100 MHz, CDCl3): d=
191.41, 158.64, 153.78, 153.36, 137.97, 135.58, 132.87, 132.18,
130.42, 129.65, 128.66, 128.64, 128.02, 125.46, 124.72, 119.35,
117.24, 102.19; HR-MS (ESI): m/z=452.9980 ([M+H]+),
calcd. for C22H13IO3: 452.9982.
3m:[18] 1H NMR (400 MHz, CDCl3): d=7.71 (d, J=8.0 Hz,
2H), 7.64–7.60 (m, 1H), 7.48–7.46 (m, 1H), 7.35–7.34 (m,
3H), 7.30–7.23 (m, 4H), 7.17 (d, J=8.0 Hz, 2H), 2.36 (s,
3H); 13C NMR (100 MHz, CDCl3): d=191.60, 158.80,
153.73, 152.64, 144.87, 133.85, 132.54, 132.42, 129.42, 129.32,
128.71, 128.52, 127.93, 126.26, 124.57, 119.53, 117.16, 21.73.
3r:[18] 1H NMR (400 MHz, CDCl3): d=7.67–7.61 (m, 3H),
7.52–7.46 (m, 3H), 7.37–7.33 (m, 3H), 7.32–7.25 (m, 4H);
13C NMR (100 MHz, CDCl3): d=191.09, 158.64, 153.78,
153.34, 135.05, 132.88, 132.18, 131.97, 130.61, 129.65, 129.15,
128.66, 128.64, 128.02, 125.47, 124.74, 119.34, 117.22.
3n: 1H NMR (400 MHz, CDCl3): d=7.74 (d, J=8.0 Hz,
2H), 7.64–7.60 (m, 1H), 7.49–7.46 (m, 1H), 7.35–7.34 (m,
3H), 7.29–7.24 (m, 4H), 7.19 (d, J=8.0 Hz, 2H), 2.66 (q, J=
7.6 Hz, 2H), 1.22 (t, J=7.6 Hz, 3H); 13C NMR (100 MHz,
CDCl3): d=191.60, 158.80, 153.74, 152.66, 150.92, 134.07,
132.52, 132.43, 129.51, 129.38, 128.72, 128.51, 128.12, 127.93,
126.32, 124.55, 119.57, 117.15, 28.99, 14.90; HR-MS (ESI):
m/z=355.1325 ([M+H]+), calcd. for C24H18O3: 355.1329.
3s:[18] 1H NMR (400 MHz, CDCl3): d=7.74 (d, J=8.4 Hz,
2H), 7.66–7.62 (m, 1H), 7.49–7.47 (m, 1H), 7.37–7.31 (m,
5H), 7.30–7.25 (m, 4H); 13C NMR (100 MHz, CDCl3): d=
190.85, 158.64, 153.79, 153.28, 140.32, 134.66, 132.85, 132.20,
130.54, 129.63, 128.98, 128.64, 128.00, 125.54, 124.71, 119.35,
117.23.
3o: 1H NMR (400 MHz, CDCl3): d=7.72 (d, J=8.0 Hz,
2H), 7.64–7.60 (m, 1H), 7.48–7.46 (m, 1H), 7.35–7.33 (m,
3H), 7.30–7.23 (m, 4H), 7.17 (d, J=8.0 Hz, 2H), 2.62 (t, J=
7.6 Hz, 2H), 1.60–1.54 (m, 2H), 1.37–1.28 (m, 2H), 0.92 (t,
J=7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=191.64,
158.82, 153.73, 152.66, 149.71, 134.03, 132.54, 132.43, 129.43,
129.39, 128.73, 128.65, 128.50, 127.93, 126.29, 124.57, 119.54,
117.16, 35.76, 33.01, 22.27, 13.84; HR-MS (ESI): m/z=
383.1637 ([M+H]+), calcd. for C26H22O3: 383.1642.
3t:[18] 1H NMR (400 MHz, CDCl3): d=7.85–7.81 (m, 2H),
7.66–7.61 (m, 1H), 7.49–7.47 (m, 1H), 7.37–7.31 (m, 3H),
7.30–7.25 (m, 4H), 7.06–7.02 (m, 2H); 13C NMR (100 MHz,
CDCl3): d=190.45, 166.09 (d, J=254.8 Hz), 158.67, 153.77,
153.07, 132.79, 132.77 (d, J=2.9 Hz), 132.26, 131.93 (d, J=
9.6 Hz), 129.58, 128.65, 128.61, 127.98, 125.70, 124.69, 119.37,
117.22, 115.83 (d, J=22.1 Hz).
3p: 1H NMR (400 MHz, CDCl3): d=7.75 (d, J=8.4 Hz,
2H), 7.64–7.60 (m, 1H), 7.49–7.47 (m, 1H), 7.40–7.35 (m,
5H), 7.30–7.24 (m, 4H), 1.30 (s, 9H); 13C NMR (100 MHz,
CDCl3): d=191.61, 158.85, 157.64, 153.73, 152.77, 133.75,
132.53, 132.43, 129.37, 129.23, 128.73, 128.51, 127.96, 126.33,
3u: 1H NMR (400 MHz, CDCl3): d=8.80 (d, J=8.4 Hz,
2H), 7.93 (d, J=8.0 Hz, 1H), 7.87 (d, J=7.2 Hz, 1H), 7.80
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(d, J=8.0 Hz, 1H), 7.57–7.47 (m, 2H), 7.37 (t, J=7.6 Hz,
1H), 7.31 (s, 1H), 7.26–7.15 (m, 6H), 7.09–7.07 (m, 1H),
2.79 (q, J=7.6 Hz, 2H), 1.31 (t, J=7.6 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=193.78, 159.14, 154.02, 152.88, 150.45,
134.21, 133.79, 133.77, 132.73, 131.43, 130.57, 129.00, 128.50,
128.38, 128.34, 128.19, 127.90, 126.51, 126.48, 125.94, 124.65,
124.06, 117.40, 116.08, 28.92, 15.04; HR-MS (ESI): m/z=
405.1482 ([M+H]+), calcd. for C28H20O3: 405.1485.
3z: 1H NMR (400 MHz, CDCl3): d=7.65–7.61 (m, 1H),
7.47–7.45 (m, 1H), 7.42–7.34 (m, 4H), 7.28–7.19 (m, 6H);
13C NMR (100 MHz, CDCl3): d=189.67, 158.13, 153.84,
153.30, 137.91, 133.16, 133.11, 132.71, 132.48, 131.57, 131.18,
130.68, 129.53, 128.61, 128.34, 128.32, 126.31, 124.68, 119.53,
117.21; HR-MS (ESI): m/z=395.0236 ([M+H]+), calcd. for
C22H12Cl2O3: 395.0236.
3v:[10k] 1H NMR (400 MHz, CDCl3): d=7.63–7.56 (m,
2H), 7.48–7.46 (m, 1H), 7.34–7.29 (m, 4H), 7.24–7.21 (m,
4H), 7.16–7.11 (m, 2H), 2.40 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=193.68, 158.76, 153.72, 152.21, 140.14, 136.01,
132.55, 132.46, 132.37, 131.92, 131.04, 129.26, 128.54, 128.44,
127.91, 127.54, 125.49, 124.54, 119.62, 117.13, 21.21.
3aa:[10k] 1H NMR (400 MHz, CDCl3): d=7.73 (d, J=
8.8 Hz, 2H), 7.36–7.32 (m, 5H), 7.27–7.23 (m, 3H), 7.18–
7.16 (m, 1H), 7.08–7.06 (m, 1H), 2.50 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=191.11, 158.90, 153.88, 153.46, 144.48,
140.19, 134.81, 132.43, 130.55, 129.54, 128.93, 128.62, 128.59,
127.71, 125.96, 124.34, 117.33, 116.90, 21.72.
3w: 1H NMR (400 MHz, CDCl3): d=7.63–7.60 (m, 1H),
7.50–7.45 (m, 2H), 7.34–7.22 (m, 9H), 7.18–7.15 (m, 1H);
13C NMR (100 MHz, CDCl3): d=190.77, 158.34, 153.77,
152.53, 136.54, 133.06, 132.86, 132.74, 132.59, 131.58, 130.54,
129.33, 128.51, 128.39, 128.21, 127.02, 126.83, 124.57, 119.68,
117.15; HR-MS (ESI): m/z=361.0630 ([M+H]+), calcd. for
C22H13ClO3: 361.0626.
1
3ab: H NMR (400 MHz, CDCl3): d=7.63–7.59 (m, 1H),
7.48–7.46 (m, 1H), 7.34–7.31 (m, 4H), 7.25–7.20 (m, 4H),
7.12–7.10 (m, 1H), 7.00–6.98 (m, 1H), 2.34 (s, 3H) 2.26 (s,
3H); 13C NMR (100 MHz, CDCl3): d=193.81, 158.78,
153.73, 152.04, 136.95, 135.99, 134.96, 133.16, 132.53, 132.51,
131.81, 131.45, 129.22, 128.52, 128.42, 127.92, 127.67, 124.54,
119.68, 117.12, 20.74, 20.71; HR-MS (ESI): m/z=355.1325
([M+H]+), calcd. for C24H18O3: 355.1329.
3x:[10k] 1H NMR (400 MHz, CDCl3): d=7.65–7.59 (m,
3H), 7.49–7.47 (m, 1H), 7.36–7.34 (m, 3H), 7.31 (s, 1H),
7.29–7.24 (m, 5H), 2.34 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=192.20, 158.78, 153.75, 152.78, 138.41, 136.26,
134.66, 132.59, 132.40, 129.57, 129.43, 128.70, 128.53, 128.45,
127.96, 126.66, 126.23, 124.60, 119.52, 117.19, 21.21.
4:[24] 1H NMR (400 MHz, CDCl3): d=8.08 (d, J=7.6 Hz,
2H), 7.56 (t, J=7.2 Hz, 1H), 7.45 (t, J=7.6 Hz, 2H), 1.81–
1.67 (m, 3H), 1.60–1.56 (m, 2H), 1.47–1.44 (m, 1H), 1.27 (s,
6H), 1.12 (s, 6H); 13C NMR (100 MHz, CDCl3): d=166.33,
132.83, 129.77, 129.53, 128.45, 60.38, 39.10, 31.97, 20.86,
17.02; HR-MS (ESI): m/z=262.1806 ([M+H]+), calcd. for
C16H23NO2: 262.1802.
3y:[10k] 1H NMR (400 MHz, CDCl3): d=7.90 (s, 1H), 7.72–
7.62 (m, 3H), 7.50–7.47 (m, 1H), 7.37–7.27 (m, 8H);
13C NMR (100 MHz, CDCl3): d=190.76, 158.57, 153.81,
153.56, 137.97, 136.57, 132.97, 132.15, 131.97, 130.16, 129.68,
128.68, 128.65, 128.07, 127.75, 125.25, 124.76, 122.86, 119.30,
117.26.
5:[7b] 1H NMR (400 MHz, CDCl3): d=8.05 (d, J=7.6 Hz,
2H), 7.57 (t, J=7.2 Hz, 1H), 7.48 (t, J=7.6 Hz, 2H), 7.06 (s,
2H), 5.13 (s, 1H), 4.21 (s, 2H), 1.43 (s, 18H); 13C NMR
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(100 MHz, CDCl3): d=198.29, 152.70, 137.00, 136.04, 132.92,
128.58, 128.53, 126.14, 125.01, 45.23, 34.29, 30.27.
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Acknowledgements
We gratefully acknowledge the National Natural Science
Foundation of China (No. 21572078, 21202057), the Natural
Science Foundation of Anhui (No. 1308085MB25) and Scien-
tific Research Foundation of Anhui University of Science and
Technology (No. ZY538) for financial support of this work.
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12 Visible Light-Induced Decarboxylative Acylarylation of
Phenyl Propiolates with a-Oxocarboxylic Acids to
Coumarins Catalyzed by Hypervalent Iodine Reagents
under Transition Metal-Free Conditions
Adv. Synth. Catal. 2017, 359, 1 – 12
Shuai Yang, Hui Tan, Wangqin Ji, Xiangbiao Zhang,*
Pinhua Li, Lei Wang*
Adv. Synth. Catal. 0000, 000, 0 – 0
12
ꢁ 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÞÞ
These are not the final page numbers!