Synthesis of Acyl Azides from 1,3-Diketones via Oxidative Cleavage of Two C-C Bonds

Article abstract of DOI:10.1021/acs.joc.8b01417

A metal-free PhI(OAc)₂-mediated method for the synthesis of acyl azides through oxidative cleavage of 1,3-diketones is described. This method is shown to have a broad substrate scope, providing a useful tool for multiproduct synthesis in a single procedure. A possible reaction pathway is proposed based on mechanistic studies.

Full text of DOI:10.1021/acs.joc.8b01417

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Note
Synthesis of Acyl Azides from 1,3-Diketones
via Oxidative Cleavage of Two C-C Bonds
Tian-Yang Yu, Zhao-Jing Zheng, Tong-Tong Dang, Fang-Xia Zhang, and Hao Wei
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b01417 • Publication Date (Web): 06 Aug 2018
Downloaded from http://pubs.acs.org on August 6, 2018
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Synthesis of Acyl Azides from 1,3ꢀDiketones via Oxidative
Cleavage of Two C−C Bonds
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TianꢀYang Yu†,§, ZhaoꢀJing Zheng‡,§, TongꢀTong Dang†, FangꢀXia Zhang†
and Hao Wei*,†
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† Key Laboratory of Synthetic and Natural Functional Molecular Chemistry of the
Ministry of Education, College of Chemistry & Materials Science, Northwest
University, Xi’an 710127, P. R. China
‡ State Key Laboratory of Applied Organic Chemistry College of Chemistry and
Chemical Engineering Lanzhou University, Lanzhou 730000, P. R. China
ABSTRACT: A metalꢀfree PhI(OAc)2ꢀmediated method for the synthesis of acyl
azides through oxidative cleavage of 1,3ꢀdiketones is described. This method is shown
to have a broad substrate scope, providing a useful tool for multiproduct synthesis in
single procedure. A possible reaction pathway is proposed based on mechanistic studies
C−C bonds are one of the most fundamental chemical bonds in organic compounds.
As compared to C−C bondꢀforming reactions, reactions for formation of C−X bonds
through the selective cleavage of C−C bonds remain a major challenge.1,2 The cleavage
of unstrained C−C bonds with subsequent functionalization would not only provide
unusual retrosynthetic disconnections, but also improve industrial processes.
Traditionally, harsh conditions with highꢀcosting transitionꢀmetal catalysts and
stoichiometric oxidants are required to cleave C−C bonds. Thus, the development of
green approaches toward unstrained C−C bond cleavage is highly desirable.
1,3ꢀDicarbonyl moieties are found in various natural products, drugs, and biologically
active compounds. Despite the thermodynamic stability of C−C bonds, the oxidative
cleavage of 1,3ꢀdiketones has evolved into a powerful tool for synthesis of carboxylic
acids.3 Also, several elegant examples of the construction of new C−C,4 C−O,5 C−N6 or
other bonds7 have been reported through fragmentation of 1,3ꢀdicarbonyl compounds.
On the other hand, acyl azides are valuable intermediates in synthesis and building
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blocks in organic chemistry.8 Classical procedures for synthesis of acyl azides are based
on combining activated acid derivatives (acyl chlorides, anhydrides and Nꢀacyl
benzotriazoles) with metal azides.9 To our knowledge, no examples of acyl azide
preparation through the direct oxidative cleavage of 1,3ꢀdiketones under metalꢀfree
conditions have been reported previously. Herein, we disclose the development of a
method for the oxidative cleavage of 1,3ꢀdiketone compounds, which provides facile
access to a series of functionalized acyl azides (Scheme 1).
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Scheme 1. Synthesis of two azides.
Initially, we investigated the reaction of compound (1a) in the presence of
(diacetoxyiodo)benzene, NaBr, K2CO3, and NaN3 in different solvents. Among these
solvents, acetone gave the most promising results, but the yields were not high (Table 1,
entries 1–3). It was found that aqueous solutions of acetone were required to obtain
higher product yields, probably due to the low solubility of sodium azide in organic
solvents (Table 1, entries 4 and 5). This result encouraged us to further optimize with
the volume of water used. To our delight, acyl azide 2a was obtained in 60% yield in
acetone/H2O (5:1, v/v) (Table 1, entry 5). Other hypervalent iodine(III) reagents, such
as [bis(trifluoroacetoxy)iodo]benzene and iodobenzene dichloride, were also examined,
but were found to be less efficient than PhI(OAc)2 (Table 1, entries 5–7). Next, NaI,
NH4Br and CuBr were tested as additives, with the results showing that NaBr was the
best option (Table 1, entries 5, 8−10). Finally, a screening of different bases showed that
NaOAc was slightly superior to K2CO3 (Table 1, entries 5, 11–13).
Table 1. Optimization of PhI(OAc)2ꢀmediated cleavage of 1,3ꢀdiketonesa
Entry
Oxidant
addtive
base
Yieldb (%)
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1c
2d
3e
4f
PhI(OAc)2
NaBr
NaBr
NaBr
NaBr
NaBr
NaBr
K2CO3
23
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OCOCF
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
21
trace
44
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5g
6g
60
trace
)
3 2
7g
PhICl2
NaBr
NaI
K2CO3
K2CO3
K2CO3
K2CO3
Na2CO3
NaOAc
ꢀꢀꢀ
43
8g
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
46
9g
NH4Br
CuBr
NaBr
NaBr
NaBr
45
10g
11g
12g
13g
trace
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67
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aReaction conditions: 1a (0.2 mmol), oxidant (0.44 mmol), additive (0.5 mmol), base
(0.2 mmol) and NaN3 (0.8 mmol) in the indicated solvent (1.0 mL) at 50 °C for 4 h.
bYields were determined by H NMR with 1,1,2,2ꢀtetrachloroethane as an internal
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standard. cIn acetone. dIn CH3CN. eIn DCE. fIn the solvent of acetone and H2O (10:1,
V/V). gIn the solventof acetone and H2O (5:1, V/V).
Next, the generality of the method was then investigated using a variety of
symmetrical 1,3ꢀ diketones (Scheme 2). In general, the reaction was effective for a
broad range of 1,3ꢀ diketones, affording acyl azide products in moderate to good yields.
This reaction exhibited excellent compatibility with a variety ofsubstituents, including
aryl halides (2f, 2g, and 2i), ethers (2a and 2e), heteroaromatics (2l and 2m), nitrile (2h),
and 2ꢀnaphthoyl (2j).
Scheme 2. Substrate scope of symmetric 1,3ꢀdiketonea
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a
Reaction conditions: 1 (0.2 mmol), PhI(OAc)2 (0.44 mmol), NaBr (0.5 mmol),
NaOAc (0.2 mmol) and NaN3 (0.8 mmol) in acetone/H2O (5/1, V/V) (1.0 mL) at 50 °C
for 4 h, yields were determined by H NMR with 1,1,2,2ꢀtetrachloroethane as an
internal standard.
1
To further explore the generality of this azidation method, we applied this
fragmentation reaction to various unsymmetrical 1,3ꢀdiketones. As shown in Scheme 3,
all reactions proceeded smoothly, furnishing two different azides in one pot with
moderate to good yields. Importantly, these two acyl azides could be separated by
column chromatography. Unfortunately, indanedione 1y and aliphatic 1, 3ꢀdiketones
(1z and 1za) did not react smoothly under the optimized reaction conditions.
Scheme 3. Substrate scope of unsymmetrical 1,3ꢀdiketonesa
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aReaction conditions: diketone (0.2 mmol), PhI(OAc)2 (0.44 mmol), NaBr (0.5 mmol),
NaOAc (0.2 mmol) and NaN3 (0.8 mmol) in acetone/H2O (5/1, V/V) (1.0 mL) at 50 °C
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for 4 h, yields were determined by H NMR with 1,1,2,2ꢀtetrachloroethane as an
internal standard.
A series of control experiments were performed to investigate the reaction pathway.
The reaction of 1a was initially conducted under the optimal conditions, but with a
shorter reaction time, which resulted in diazido intermediate 3 and desired product 2a
being obtained in 24% and 30% yields, respectively (Scheme 4a). Furthermore, treating
diazides 4 with NaN3 led to smooth fragmentation of the dicarbonyl core, without the
need for additional reagents. These results indicated that the reaction proceeded via an
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intermediate diazido 1,3ꢀdiketone. Moreover, we noticed that NaN3 (0.2 mmol)
generated acyl azide (0.28 mmol), which indicated that a part of azido of products
originated from the diazido 1,3ꢀdiketone intermediate itself. Other nucleophiles were
tested to demonstrate the transformation of the diazido intermediate. As shown in
Scheme 4c, the reaction of diazides 4 (0.3 mmol) with benzylamine (0.2 mmol)
afforded amide 2f’ (0.11 mmol) and 2a’(0.066mmol), in addition to acyl azides 2f
(0.036 mmol) and 2a (0.020 mmol).
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Scheme 4. Control experiments
Based on control experiments and related reports,10,11 a possible reaction pathway is
outlined in Scheme 5. The reaction begins with the oxidative dibromination of diketone
1, which produces dibrominated diketone M1. Next, intermediate M2 is formed via
nucleophilic substitution of M1 with NaN3. Nucleophilic attack on the carbonyl group
then leads to C−C bond cleavage of M2 and formation of the acyl azide and M3. Finally,
M3 undergoes a rearrangement to produce another acyl azide molecule with the release
of N2 and a cyanide ion.
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Scheme 5. Possible reaction pathway
In summary, a novel, atomꢀeconomical strategy for generating acyl azides from the
cleavage of two C−C bonds in 1,3ꢀdiketones has been developed. The use of
environmentally friendly hypervalent iodine(III) reagent (PhI(OAc)2) under aerobic
conditions makes this protocol green and highly practical. Furthermore, this chemistry
provides an approach to a new methodologically diverse synthetic strategy for
obtaining two differently substituted acyl azides in one pot from unsymmetrical
1,3ꢀdiketones. Several experiments were performed to investigate the possible
pathway. This simple and practical method complements classical acyl azide
preparation methods and provides new ideas for the design of novel 1,3ꢀdiketone
transformations.
Experimental Section
General Information: Commercial reagents and solvents were purchased from TCI,
Strem Chemicals and Alfa Aesar. Deuterated solvents were purchased from Cambridge
Isotope Laboratories, Inc. and were stored over 4Å molecular sieves prior to use. Flash
column chromatography was carried out using silica gel (200–300 mesh) at increased
pressure. NMR spectra were recorded on WNMRꢀI spectrometer and JEOL
JNMꢀECZ600R/S3 spectrometer. The spectra were recorded in CDCl3 or other solvents
at room temperature. 1H and 13C chemical shifts are reported in ppm relative to either
the residual solvent peak (13C) or TMS (1H) as an internal standard. MS were performed
on Bruker Daltonics MicroTofꢀQ II mass spectrometer and SHIMADZU
GCMSꢀQP2010. IR spectra were recorded using Bruker Tensor27 FTꢀIR instrument
and are reported in wavenumbers (cmꢀ1).
Caution! Acyl azide and cyanide may cause potentially damage and should be
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carefully handled. The maximum reaction scale was limited to 0.2 mmol. Protective
gear was needed with larger scales. The temperature of water bath of rotary evaporator
was 35 °C.
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General procedure for the synthesis of acyl azides: A mixture of ketone 112 (0.2
mmol), PhI(OAc)2 (0.44 mmol), NaBr (0.5 mmol), NaN3 (0.8 mmol) and NaOAc (0.2
mmol) in 1 mL solvent (acetone : water = 5:1) was stirred at 50 oC. After 4 hours, the
mixture was cooled to room temperature and diluted with Et2O, washed with water and
brine. Then the solution was dried with sodium sulfate anhydrous, concentrated using
rotary evaporator. The residue was purified by column chromatography to provide the
acyl azide 2.
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4ꢀmethoxybenzoyl azide (2a).13a White solid (67% yield, 47.4 mg); H NMR (400
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MHz, CDCl3): δ 7.98 (d, J = 9.2 Hz, 2H), 6.92 (d, J = 8.8 Hz, 2H), 3.87 (s, 3H); C
NMR (100 MHz, CDCl3): δ 171.6, 164.6, 131.7, 123.2, 113.9, 55.5; FTꢀIR (KBr): 2137,
1680, 1598, 1318, 985 cmꢀ1; MS (EI) m/z: 177.0 (31) [M]+, 149 (63) [MꢀN2]+.
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4ꢀmethylbenzoyl azide (2b).13a Colorless oil (75% yield, 48.2 mg); H NMR (400
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MHz, CDCl3): δ 7.91 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.0 Hz, 2H), 2,41 (s, 3H); C
NMR (100 MHz, CDCl3): δ 172.3, 145.4, 129.5, 129.3, 128.0, 21.7; FTꢀIR (KBr): 2136,
1691, 1255, 1023, 735 cmꢀ1; MS (EI) m/z: 161.0 (17)[M]+, 133.0 (28)[MꢀN2]+.
Benzoyl azide (2c).13a Colorless oil (55% yield, 32.3 mg); 1H NMR (400 MHz, CDCl3):
δ 8.03 (d, J = 7.2 Hz, 2H), 7.62 (t, J = 7.2 Hz, 1H), 7.46 (t, J = 7.6 Hz, 2H); 13C NMR
(100 MHz, CDCl3): δ 172.5, 134.5, 130.7, 129.4, 128.6; FTꢀIR (KBr): 2139, 1691, 1242,
1191, 993, 700 cmꢀ1; MS (EI) m/z : 147.1 (31) [M]+, 123.1 (72) [MꢀN2]+.
4ꢀ(tertꢀbutyl)benzoyl azide (2d).13a White solid (69% yield, 56.1 mg); 1H NMR (600
MHz, CDCl3): δ 7.95 (d, J = 8.4 Hz, 2H), 7.46 (d, J = 9.0 Hz, 2H), 1.33 (s, 9H); 13C
NMR (150 MHz, CDCl3): δ 172.2, 158.2, 129.3, 127.9, 125.6, 35.2, 31.0; FTꢀIR (KBr):
2967, 2132, 1693, 1258, 689 cmꢀ1; MS (EI) m/z: 203.0 (26) [M]+, 161.1 (100) [MꢀN3]+.
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3ꢀmethoxybenzoyl azide (2e).13a Colorless oil (60% yield, 42.2 mg). H NMR (600
MHz, CDCl3): δ 7.63 − 7.61 (m, 1H), 7.54 − 7.53 (m, 1H), 7.35 (t, J = 8.4 Hz, 1H),
7.17−7.15 (m, 1H), 3.85 (s, 3H); 13C NMR (150 MHz, CDCl3): δ 172.3, 159.7, 131.9,
129.6, 121.9, 121.0, 113.5, 55.4; FTꢀIR (KBr): 2141, 1696, 1599, 1271, 1047, 678 cmꢀ1;
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MS (EI) m/z: 177.0 (31) [M]+, 149.1 (63) [MꢀN2]+.
4ꢀchlorobenzoyl azide (2f).13a White solid (50% yield, 36.1 mg). 1H NMR (600 MHz,
CDCl3): δ 7.96 (d, J = 8.4 Hz, 2H), 7.43 (d, J = 8.4 Hz, 2H); 13C NMR (150 MHz,
CDCl3): δ 171.5, 140.9, 132.3, 130.8, 129.0; FTꢀIR (KBr): 2136, 1682, 1253, 995, 744
cmꢀ1; MS (EI) m/z: 181.0 (3) [M]+, 153.0 (14) [MꢀN2]+, 139.0 (100) [MꢀN3]+.
4ꢀbromobenzoyl azide (2g).13a White solid (41% yield, 36.8 mg). 1H NMR (600 MHz,
CDCl3): δ 7.88 (d, J = 8.4 Hz, 2H), 7.60 (d, J = 9.0 Hz, 2H); 13C NMR (150 MHz,
CDCl3): δ 171.7, 132.0, 130.8, 129.7, 129.5; FTꢀIR (KBr): 2134, 1680, 1534, 1250, 991,
740 cmꢀ1; MS (EI) m/z: 224.9 (14) [M]+, 196.9 (30) [MꢀN2]+, 182.9 (100) [MꢀN3]+.
4ꢀcyanobenzoyl azide (2h).13a White solid (26% yield, 28.0 mg). 1H NMR (600 MHz,
CDCl3): δ 8.13 (d, J = 8.4 Hz, 2H), 7.76 (d, J = 9.0 Hz, 2H); 13C NMR (150 MHz,
CDCl3): δ 171.7, 134.1, 132.4, 129.8, 117.6, 117.5; FTꢀIR (KBr): 2230, 2139, 1698,
1245, 1024, 678 cmꢀ1; MS (EI) m/z: 172.0 (4) [M]+, 144.0 (54) [MꢀN2]+, 130.0 (100)
[MꢀN3]+.
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3ꢀchlorobenzoyl azide (2i). Colorless oil (40% yield, 28.9 mg). 1H NMR (600 MHz,
CDCl3): δ 8.00 (t, J = 1.8 Hz, 1H), 7.91 (dt, J = 1.8 Hz, 7.8 Hz, 1H), 7.59 − 7.57 (m, 1H),
13
7.40 (t, J = 7.8 Hz, 1H); C NMR (150 MHz, CDCl3): δ 171.3, 134.9, 134.2, 132.2,
129.9, 129.4, 127.5; FTꢀIR (KBr): 2140, 1696, 1237, 1002, 728 cmꢀ1; MS (EI) m/z:
181.0(16) [M]+, 139.0(100) [MꢀN3]+.
1
2ꢀnaphthoyl azide (2j).13b White solid (65% yield, 51.1 mg). H NMR (600 MHz,
CDCl3): δ 8.57 (s, 1H), 8.01 (dd, J = 1.8 Hz, 8.4 Hz, 1H), 7.93 (d, J = 8.4 Hz, 1H), 7.87
− 7.85 (m, 2H), 7.62 − 7.59 (m, 1H), 7.55 − 7.53 (m, 1H); 13C NMR (150 MHz, CDCl3):
δ 172.5, 136.1, 132.3, 131.4, 129.6, 128.9, 128.5, 127.8, 127.8, 126.9, 124.5; FTꢀIR
(KBr): 2139, 1685, 1200, 996, 722 cmꢀ1; MS (EI) m/z: 197.0 (10) [M]+; 169.0 (100)
[MꢀN2]+.
3,4ꢀdimethoxybenzoyl azide (2k).13c White solid (65% yield, 26.8 mg). 1H NMR (400
MHz, CDCl3): δ 7.67 (d, J = 8.4 Hz, 1H), 7.51 (s, 1H), 6.88 (d, J = 8.8 Hz, 1H), 3.95 (s,
13
3H), 3.93 (s, 3H); C NMR (100 MHz, CDCl3): δ 171.6, 154.2, 148.8, 123.9, 123.2,
111.3, 110.2, 56.0, 55.9; FTꢀIR (KBr): 2137, 1675, 1267, 1020, 644 cmꢀ1; MS (EI) m/z:
207.0 (8) [M]+; 179.0 (54) [MꢀN2]+.
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Furanꢀ2ꢀcarbonyl azide (2l).13d White solid (42% yield, 22.8 mg). 1H NMR (600 MHz,
CDCl3): δ 7.66 (dd, J = 1.2 Hz, 1.5Hz, 1H), 7.28 − 7.21 (m, 1H), 6.56 − 6.55 (m, 1H);
13C NMR (150 MHz, CDCl3): δ 162.5, 148.1, 145.5, 120.0, 112.5; FTꢀIR (KBr): 2142,
1686, 1290, 1030, 789 cmꢀ1; MS (EI) m/z: 137(18) [M]+, 109 (59) [MꢀN2]+.
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Thiopheneꢀ2ꢀcarbonyl azide (2m).13a White solid (61% yield, 37.1 mg). H NMR
(600 MHz, CDCl3): δ 7.84 (dd, J = 3.6 Hz, 1.2 Hz, 1H), 7.66 (dd, J = 5.4 Hz, 1.2 Hz,
1H), 7.14 (dd, J = 4.8 Hz, 3.6 Hz, 1H); 13C NMR (150 MHz, CDCl3): δ 166.6, 134.8,
134.7, 134.4, 128.4; FTꢀIR (KBr): 2156, 1685, 1519, 1255, 739 cmꢀ1; MS (EI) m/z:
153.0 (24) [M]+, 125.1 (34) [MꢀN2]+, 111.0 (100) [MꢀN3]+.
Benzothiopheneꢀ2ꢀcarbonyl azide (2n).13e White solid (53% yield, 21.6 mg). H
1
NMR (400 MHz, CDCl3): δ 8.10 (s, 1H), 7.88 (t, J = 8.8 Hz, 2H), 7.51 − 7.41 (m, 2H);
13C NMR (100 MHz, CDCl3): δ 167.6, 143.0, 138.7, 134.7, 131.7, 127.8, 126.0, 125.2,
122.9; FTꢀIR (KBr): 2158, 1668, 1514, 1243, 758 cmꢀ1; MS (EI) m/z: 203(100) [M]+.
Mechanism study: A mixture of ketone (0.2 mmol), PhI(OAc)2 (0.44 mmol), NaBr
(0.5 mmol), NaN3 (0.8 mmol) and NaOAc (0.2 mmol) in 1 mL solvent (acetone : water
= 5:1) was stirred at 50 oC for 10 min. The mixture was cooled to room temperature and
diluted with Et2O. The solution was washed with water and brine. Then the solution
was dried with sodium sulfate anhydrous, concentrated using rotary evaporator. The
residue was purified by column chromatography to provide the acyl azide 2a (21.2 mg)
and compound 3 (17.3 mg).
A mixture of 4 (0.2 mmol) and NaN3 (0.2 mmol) in 1 mL solvent (acetone: water =
o
5:1) was stirred at 50 C for 4 h. The mixture was cooled and purified by column
chromatography on silica gel to provide the acyl azide 2a (0.11 mmol) and acyl azide 2f
(0.16 mmol), yields were determined by 1H NMR with 1,1,2,2ꢀtetrachloroethane as an
internal standard.
A mixture of 4 (0.3 mmol) and benzylamine (0.2 mmol) in 2 mL benzene was
stirred at 50 oC for 5 h. The mixture was cooled and purified by column
chromatography on silica gel to provide the acyl azide 2a (0.020 mmol), 2f (0.036
1
mmol) and amide 2f’ (0.11 mmol), 2a’ (0.066 mmol), yields were determined by H
NMR with 1,1,2,2ꢀtetrachloroethane as an internal standard.
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2,2ꢀdiazidoꢀ1,3ꢀbis(4ꢀmethoxyphenyl)propaneꢀ1,3ꢀdione (3). White solid (24%
yield, 17.3 mg). 1H NMR (400 MHz, CDCl3): δ 8.00 (d, J = 8.8 Hz, 4H), 6.84 (d, J = 9.2
Hz, 4H), 3.82 (s, 6H); 13C NMR (100 MHz, CDCl3): δ 187.0, 164.5, 133.0, 125.1, 114.0,
88.5, 55.5; HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C17H14N6NaO4 389.0969;
Found 389.0963.
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2,2ꢀdiazidoꢀ1ꢀ(4ꢀchlorophenyl)ꢀ3ꢀ(4ꢀmethoxyphenyl)propaneꢀ1,3ꢀdione (4).White
solid (30% yield, 22.1 mg). 1H NMR (400 MHz, CDCl3): δ 7.99 − 7.93 (m, 4H), 7.35 (d,
J = 8.4 Hz, 2H), 6.85 (d, J = 8.8 Hz, 2H), 3.83 (s, 3H); 13C NMR (100 MHz, CDCl3): δ
187.9, 186.7, 164.7, 141.2, 133.0, 131.7, 130.6, 129.1, 124.9, 114.1, 88.1, 55.5; FTꢀIR
(KBr): 2113, 1679, 1594, 1272, 889 cmꢀ1; MS (EI) m/z: 314 (0.36) [MꢀN2ꢀN2]+, 316
(0.12); HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C16H11ClN6NaO3 393.0473 Found
393.0478.
Nꢀbenzylꢀ4ꢀmethoxybenzamide (2a’).13f White solid (55% yield, 15.1 mg). 1H NMR
(400 MHz, CDCl3): δ 7.76 (d, J = 8.8 Hz, 2H), 7.34−7.26 (m, 5H), 6.90 (d, J = 8.4 Hz,
2H), 6.51 (s, 1H), 4.61 (d, J = 5.6 Hz, 2H), 3.83 (s, 3H); 13C NMR (100 MHz, CDCl3):
δ 166.8, 162.1, 138.4, 128.7, 128.7, 127.8, 127.5, 126.6, 113.7, 55.4, 44.0.
1
Nꢀbenzylꢀ4ꢀchlorobenzamide (2f’).13f White solid (33% yield, 26.8 mg). H NMR
(400 MHz, CDCl3): δ 7.72 (d, J = 8.8 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.35−7.30 (m,
5H), 6.53 (s, 1H), 4.61 (d, J = 5.2 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 166.3, 137.9,
137.8, 132.7, 128.8, 128.4, 127.9, 127.7, 44.2.
The oneꢀpot transformation of compound 2i: A mixture of ketone (0.2 mmol),
PhI(OAc)2 (0.44 mmol), NaBr (0.5 mmol), NaN3 (0.8 mmol) and NaOAc (0.2 mmol) in
1 mL solvent (acetone : water = 5:1) was stirred at 50 oC for 4 h. After the reaction was
complete, the mixture was cooled to room temperature and diluted with Et2O. The
solution was washed with H2O and NaCl (sat.). Then the solution was dried with
Na2SO4, concentrated using rotary evaporator. The residue was transferred to a schlenk
tube and the tube was evacuated and backfilled with N2 three times before the addition
of toluene (1.0 mL). The mixture was heated at 100 oC for 1 hour. Then,
(4ꢀmethoxyphenyl)methanamine (0.4 mmol) was added and the mixture was stirred at
room temperature overnight. The mixture was concentrated under reduced pressure and
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purified
by
column
chromatography
to
provide
the
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1ꢀ(3ꢀchlorophenyl)ꢀ3ꢀ(4ꢀmethoxybenzyl)urea.
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1ꢀ(3ꢀchlorophenyl)ꢀ3ꢀ(4ꢀmethoxybenzyl)urea. White solid (13.5 mg, 23%). 1H NMR
(400 MHz, d6ꢀDMSO): δ 8.78 (s, 1H), 7.73 (s, 1H), 7.30ꢀ7.22 (m, 4H), 6.99ꢀ6.93 (m,
3H), 6.67 (t, J = 5.6 Hz, 1H), 4.27 (d, J = 6.0 Hz, 2H), 3.78 (s, 3H); 13C NMR (100 MHz,
d6ꢀDMSO): δ 158.2, 154.9, 142.1, 133.1, 132.0, 130.2, 128.5, 120.7, 117.0, 116.0,
113.7, 55.1, 42.2. HRMS (ESIꢀTOF) m/z: [M + Na]+ Calcd for C15H15ClN2NaO2
313.0714; Found 313.0708.
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ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the ACS Publications
website.
Detection of cyanide, 1H and 13C NMR spectra (PDF)
AUTHOR INFORMATION
Corresponding Author
*Email: haow@nwu.edu.cn.
Author Contributions
§These authors contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We are grateful to the financial support from the National Natural Science Foundation
of China (NSFC 21502149), the Key Science and Technology Innovation Team of
Shaanxi Province (2017KCTꢀ37) and Scientific Research Program Funded by Shaanxi
Provincial Education Department (Program No. 17JS129 and 17JK0773).
REFERENCES
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