Gold-catalyzed cyclization of 3-(2′-azidoaryl)-1-arylpropargyl carbonates or 3-aryl-1-(2′-azidoaryl)propargyl carbonates to produce quinolines

Article abstract of DOI:10.1021/jo401324k

A gold-catalyzed cyclization of 3-(2′-azidoaryl)-1-arylpropargyl carbonates to generate substituted quinolines via a sequence of 3,3-rearrangement, 6-endo-trig cyclization and denitrogenation has been developed. Similar products could be obtained from 3-aryl-1-(2′-azidoaryl) propargyl carbonates under different gold catalytic conditions via a sequential 6-endo-dig cyclization, denitrogenation, and 1,2-H shift process.

Full text of DOI:10.1021/jo401324k

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Article
Gold-Catalyzed Cyclization of 3-(2'-Azidoaryl)-1-Arylpropargyl Carbonates
or 3-Aryl-1-(2'-Azidoaryl)propargyl Carbonates to Produce Quinolines
Shugao Zhu, Luling Wu, and Xian Huang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo401324k • Publication Date (Web): 22 Aug 2013
Downloaded from http://pubs.acs.org on August 24, 2013
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Gold-Catalyzed Cyclization of 3-(2'-Azidoaryl)-1-Arylpropargyl
Carbonates or 3-Aryl-1-(2'-Azidoaryl)propargyl Carbonates to
Produce Quinolines
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Shugao Zhu,a Luling Wu*a and Xian Huang§a, b
a Department of Chemistry, Zhejiang University, Hangzhou 310028, P. R. China
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032,
P. R. China
Wululing@zju.edu.cn
Abstract:
A gold-catalyzed cyclization of 3-(2'-azidoaryl)-1-arylpropargyl carbonates to
generate substituted quinolines via a sequence of 3,3-rearrangement, 6-endo-trig
cyclization and denitrogenation has been developed. Similar products could be
obtained from 3-aryl-1-(2'-azidoaryl)propargyl carbonates under different gold
catalytic conditions via a sequential 6-endo-dig cyclization, denitrogenation and 1,2-H
shift process.
INTRODUCTION:
Quinolines represent an important group of heterocycles. Several quinoline
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derivatives have been found to exert important biological activities as antimalarial,
anti-inflammatory, antiasthamatic, antibacterial, antihypertensive, and tyrosine kinase
inhibiting agents.3-5 In addition, quinolines have been used for the preparation of nano
and mesostructures with enhanced electronic and photonic properties.6 Consequently,
the study on quinolines continues to be an active research area, and continuous efforts
have been directed to the development of new and efficient synthetic methods towards
quinolines.7
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In recent years, gold-catalyzed rearrangement reactions have attracted much
attention owing to their synthetic utility for the construction of natural products and
complex molecules.8 The most important and interesting rearrangement reactions are
conducted with propargyl esters; the latter can undergo 1,2-acyloxy migration9 or
3,3-rearrangement.10 Many research groups have intensively investigated this type of
reactions. The gold catalyzed 3,3-rearrangement of propargyl esters leads to the
formation of in situ carboxyallenes, which can be further converted into various
acyloxocarbenium ion intermediates by the same gold catalyst. By employing this
strategy, a variety of polycyclic compounds were prepared highly efficiently from
readily available starting materials.11
We envisioned that the in situ generated allene intermediate from
3-(2'-azidoaryl)-1-arylpropargyl carbonates might react with an intramolecular azide
group, leading to useful azacyclic compounds after a series of subsequent
transformations (Scheme 1). Herein, we report our results on tandem cationic
Au(I)-catalyzed activations of both propargylic carbonates and the in situ generated
allenylic carbonates, resulting in the expeditious formation of substituted quinolines
via sequential 3,3-rearrangement and cyclization. Furthermore, we also present our
study on the Au(I)-catalyzed cyclization of 3-aryl-1-(2'-azidoaryl)propargyl
carbonates, which was found to proceed via a distinct pathway to give similar
products (Scheme 1).
Scheme 1
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RESULTS AND DISCUSSION:
We selected 1a as the standard substrate to search for potential catalysts under
suitable reaction conditions. Treatment of propargyl carbonate 1a with 5 mol % of
Ph3PAuCl/AgSbF6 in DCE at 60oC furnished the desired 2a in 42% yield (entry 1).
When the reaction was performed at 80 °C, the yield was not improved. Other
solvents such as toluene, DMF, CH2Cl2 and CH3CN were examined with no
improvement (Table 1, entries 5-9). When THF was employed as the solvent, the
decarboxylation compound 1-azido-2-(3-methoxy-3-phenylprop-1-yn-1-yl)benzene
(5a) was isolated in 75% yield. Silver salts were screened: AgClO4 was slightly better
while AgOTf was ineffective. The reaction failed to afford the product 2a when
Ph3PAuCl or AgClO4 was used as catalyst alone (Table 1, entries 10 and 11).
However, screening of gold catalysts revealed that AuCl, AuCl3, Au(IPr)Cl and
PPh3AuNTf2 were less effective (Table 1, entries 12 -17).
Table 1. Optimization of reaction conditions for the cyclization of 1a forming
quinoline 2aa
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a Reactions were carried out on a 0.3 mmol scale in 3.0 mL of solvent under N2
b
atmosphere for the specified period of time with 5 mol% of the catalyst. Isolated
d
yields. c 75% decarboxylation compound 5a was isolated. 88% starting material was
recovered.
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Under the optimal conditions, the scope of this reaction was explored. Some
typical results are summarized in Table 2. As for substrate 1 wherein R1 is an
aromatic group such as phenyl, p-bromoylphenyl, p-fluorophenyl and
o-methoxyphenyl group, the reactions proceeded smoothly under the established
conditions, delivering the quinolines 2 in moderate yields (Table 2, entries 1–4).
However, when R1 is methyl, no expected product was observed and 86% of 1i was
recovered (Table 2, entry 9). The substituent on the azido-substituted phenyl unit (R2)
can be methyl, and chloride; R3 can be Ac and CO2Me. All of the products were
characterized by spectroscopic methods, and 2c was further confirmed by X-ray
crystallography (See Fig. S1 in Supporting Information).
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Table 2. Gold-catalyzed formation of quinolines 2a
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a Reactions were carried out using 1 (0.3 mmol)，[(PPh3)AuCl]/AgClO4 (5 mol%) in
o
b
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DCE (3 mL) at 60 C under N2 atmosphere. Isolated yields. 86% of 1i was
recovered.
Furthermore we also synthesized 3-aryl-1-(2'-azidoaryl)propargyl carbonatess 3
to examine the gold catalyzed reaction in order to get the differently substituted
quinolines. To our surprise, in the presence of 10 mol % of PPh3AuCl/AgOTf, the
reaction of 3 also afforded the quinolines 2 with substituents at different locations in
moderate yields at room temperature. Several examples are presented in Table 3. For
R, aromatic groups including p-F, p-CF3, p-Me, and p-Cl substituted phenyl groups
are applicable (Table 3, entries 2-5). After hydrolysis of 2c, we obtained
2-(4-fluorophenyl)quinolin-4(1H)-one (4c), and its structure was confirmed by X-ray
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crystallography (See Fig. S2 in Supporting Information).
Table 3 Gold-catalyzed formation of quinolines 2a
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a Reactions were carried out using 3 (0.3 mmol)，[(PPh3)AuCl]/AgOTf (10 mol%) in
b
c
DCE (3 mL) at rt under N2 atmosphere. Isolated yields. A small amount of
byproduct was observed.
Based on the above results and literature precedents, two catalytic cycles were
proposed to rationalize the above reactions which produce the same product 2a from
different substrate 1a or 3a (Scheme 2).12 The cyclization of 1a is initialed by an
Au-catalyzed [3,3]-sigmatropic rearrangement of the substrate to give an allenylic
carbonate A. Subsequently, A undergoes an Au-induced 6-endo-trig cyclization to
form intermediate B, which loses a molecule of N2 and proton to afford the quinolinyl
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gold intermediate C. Protodemetallation of C gave the product 2a (Scheme 2, top
cycle). The Au-catalyzed cyclization of 3a first involves an intramolecular
nucleophilic attack of the azide group to the Au-activated triple bonds in a 6-endo-dig
manner to give the intermediate D. Loss of a molecule of N2 leads to the formation of
a gold carbenoid E. The subsequent 1,2-H shift of E leads to the formation of a gold
intermediate G which finally transforms to the product 2a, and the cationic gold(I)
catalyst is regenerated (Scheme 2, bottom cycle).
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Scheme 2 Proposed mechanisms for the Au-catalyzed sequential reactions for the
synthesis of quinolines
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CONCLUSIONS:
In summary, we have developed two sets of gold(I) catalyzed cyclization
reactions, providing a facile synthesis of substituted quinolines from the easily
accessible
3-(2'-azidoaryl)-1-arylpropargyl
carbonates
or
3-aryl-1-(2'-azidoaryl)propargyl carbonates. Although producing the same type of
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products, mechanistically the reactions take place via different pathways. The reaction
of 3-(2'-azidoaryl)-1-arylpropargyl carbonates involves a reaction sequence of
[3,3]-sigmatropic rearrangement, 6-endo-trig cyclization and denitrogenation, while
the cyclization of 3-aryl-1-(2'-azidoaryl)propargyl carbonates proceeds via a
sequential 6-endo-dig cyclization, denitrogenation and 1,2-H shift process. Our study
that two regioisomeric substrates lead to the same type of products in the presence of
a similar gold(I) catalyst provide an interesting example of convergence in
homogenous gold catalysis.
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EXPERIMENTAL SECTION:
General: All reactions were performed under an N2 atmosphere. Anhydrous solvents
were distilled prior to use: THF was distilled from sodium wire using benzophenone
as the indicator; DMF was distilled from CaH2. Petroleum ether refers to the fraction
with the boiling point in the range 60–90 °C. All 1H NMR and 13C NMR spectra were
measured in CDCl3 with TMS as the internal standard. Chemical shifts are expressed
in ppm and J values are given in Hz. Starting materials: Propargylic alcohols were
prepared according to the literature.
General procedure for the preparation of propargylic compounds 1a-i and 3a-k.
An oven-dried Schlenk tube containing a Teflon-coated stirring bar was charged with
Pd(PPh3)2Cl2 (70 mg, 5 mol %), CuI (19 mg, 5 mol %), and substituted iodobenzene
(2 mmol). The Schlenk tube was sealed, evacuated and backfilled with N2 (3 cycles).
A solution of propargylic alcohol (2.4 mmol) in 10 mL of THF and 3 mL of Et3N was
subsequently injected to the Schlenk tube. The reaction mixture was stirred for 1 h at
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room temperature. After 1h the reaction was complete as monitored by TLC, the
reaction was quenched with an aqueous saturated solution of NH4Cl and extracted
with diethyl ether (3 × 20 mL). The combined organic phase was washed with brine
and dried over Na2SO4. Filtration, evaporation and column chromatography on silica
gel (Petroleum ether – ethyl acetate 4:1) afforded propargylic alcohols.
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To a solution of propargylic alcohol prepared above (1.0 mmol), pyridine (0.32 g, 4.0
mmol), and DMAP (22.4 mg, 0.2 mmol) in CH2Cl2 (10 mL) was added at 0 °C ethyl
chloroformate (0.44 g, 4.0 mmol). After being stirred for 2 h at room temperature, the
reaction mixture was diluted with CH2Cl2. The CH2Cl2 solution was washed with a
saturated aqueous copper sulfate solution, water, dried over anhydrous sodium sulfate,
filtered and concentrated. The residue was purified by column chromatography on
silica gel (Petroleum ether – ethyl acetate 10:1) to afford the corresponding
propargylic compounds.
3-(2-azidophenyl)-1-phenylprop-2-yn-1-yl methyl carbonate (1a): Yield: 83% (254
1
mg). Oil: H NMR (400 MHz, CDCl3): δ = 7.66-7.64 (m, 2H), 7.46-7.32 (m, 5H),
7.11-7.05 (m, 2H), 6.57 (s, 1H), 3.81 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ =
154.9, 141.6, 136.2, 133.9, 130.2, 129.2, 128.7, 127.9, 124.5, 118.6, 114.0, 90.5, 83.7,
70.1, 55.1 ppm; MS (EI, 70ev) m/z (%) 307 (M+, 8.56), 220 (100); IR (neat): 2956,
2128, 1747, 1489, 1297, 1096 cm–1; TOF HRMS (EI) calcd. for C17H13N3O3 (M+):
307.0957; found: 307.0954.
3-(2-azidophenyl)-1-(4-bromophenyl)prop-2-yn-1-yl methyl carbonate (1b): Yield:
1
77% (296 mg). Oil: H NMR (400 MHz, CDCl3): δ = 7.56-7.52 (m, 4H), 7.45 (d, J =
9.2 Hz, 1H), 7.39-7.35 (m, 1H), 7.13-7.07 (m, 2H), 6.51 (s, 1H), 3.83 (s, 3H) ppm;
13C NMR (100 MHz, CDCl3): δ = 154.8, 141.7, 135.3, 133.9, 131.9, 130.3, 129.6,
124.6, 123.5, 118.6, 113.8, 89.9, 84.0, 69.4, 55.2 ppm; MS (EI, 70ev) m/z (%) 385
(M+, 11.28), 219 (100); IR (neat): 2961, 2128, 1747, 1486, 1252, 1010 cm–1; TOF
HRMS (EI) calcd. for C17H1279Br N3O3 (M+): 385.0062; found: 385.0067.
3-(2-azidophenyl)-1-(4-fluorophenyl)prop-2-yn-1-yl methyl carbonate (1c): Yield:
1
81% (263 mg). Oil: H NMR (400 MHz, CDCl3): δ = 7.66-7.62 (m, 2H), 7.45 (d, J =
7.6 Hz, 1H), 7.38-7.33 (m, 1H), 7.12-7.06 (m, 4H), 6.54 (s, 1H), 3.82 (s, 3H) ppm;
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13C NMR (100 MHz, CDCl3): δ = 163.2 (J = 247.1 Hz), 154.8, 141.6, 133.9, 132.2 (J
= 2.9 Hz), 130.3, 130.0 (J = 8.6 Hz), 124.5, 118.6, 115.6 (J = 1.9 Hz), 113.8, 90.2,
83.9, 69.4, 55.1 ppm; MS (EI, 70ev) m/z (%) 325 (M+, 7.35), 238 (100); IR (neat):
2958, 2129, 1747, 1572, 1488, 1159 cm–1; TOF HRMS (EI) calcd. for C17H12FN3O3
(M+): 325.0863; found: 325.0869.
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3-(2-azidophenyl)-1-(2-bromophenyl)prop-2-yn-1-yl methyl carbonate (1d): Yield:
80% (308 mg). Oil: 1H NMR (400 MHz, CDCl3): δ = 7.94-7.92 (m, 1H), 7.61-7.59 (m,
1H), 7.47-7.33 (m, 3H), 7.26-7.25 (m, 1H), 7.12-7.08 (m, 2H), 6.87 (s, 1H), 3.85 (s,
3H) ppm; 13C NMR (100 MHz, CDCl3): δ = 154.5, 141.7, 135.4, 134.0, 133.0, 130.7,
130.3, 130.0, 127.8, 124.5, 123.4, 118.6, 113.9, 89.7, 84.0, 69.4, 55.2 ppm; MS (EI,
70ev) m/z (%) 385 (M+, 14.38), 219 (100); IR (neat): 2956, 2127, 1750, 1488, 1252,
1120 cm–1; TOF HRMS (EI) calcd. for C17H1279BrN3O3 (M+): 385.0062; found:
385.0063.
3-(2-azido-5-methylphenyl)-1-phenylprop-2-yn-1-yl methyl carbonate (1e): Yield:
1
74% (238 mg). Oil: H NMR (400 MHz, CDCl3): δ = 7.64 (d, J = 7.2 Hz, 2H),
7.42-7.37 (m, 3H), 7.25 (d, J = 6.0 Hz, 1H), 7.13 (d, J = 8.0 Hz, 1H), 6.98 (d, J = 7.6
Hz, 1H), 6.56 (s, 1H), 3.81 (s, 3H), 2.27 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ
= 154.9, 138.8, 136.2, 134.3, 134.2, 131.0, 129.2, 128.7, 127.9, 118.5, 113.7, 90.1,
83.8, 70.2, 55.0, 20.5 ppm; MS (EI, 70ev) m/z (%) 321 (M+, 11.46), 234 (100); IR
(neat): 2959, 2120, 1747, 1493, 1248, 1104 cm–1; TOF HRMS (EI) calcd. for
C18H15N3O3 (M+): 321.1113; found: 321.1118.
3-(2-azido-5-chlorophenyl)-1-phenylprop-2-yn-1-yl methyl carbonate (1f): Yield:
78% (266 mg). Oil: 1H NMR (400 MHz, CDCl3): δ = 7.63-7.61 (m, 2H), 7.42-7.40 (m,
4H), 7.30-7.28 (m, 1H), 7.01 (d, J = 8.8 Hz, 1H), 6.55 (s, 1H), 3.82 (s, 3H) ppm; 13C
NMR (100 MHz, CDCl3): δ = 154.8, 140.2, 135.9, 133.4, 130.2, 129.7, 129.3, 128.7,
127.8, 119.8, 115.4, 91.7, 82.3, 69.9, 55.1 ppm; MS (EI, 70ev) m/z (%) 341 (M+,
13.48), 184 (100); IR (neat): 2956, 2117, 1747, 1484, 1251, 1154, 933, 762 cm–1;
TOF HRMS (EI) calcd. for C17H1235ClN3O3 (M+): 341.0567; found: 341.0561.
3-(2-azidophenyl)-1-phenylprop-2-yn-1-yl acetate (1g): Yield: 76% (221 mg). Oil:
1H NMR (400 MHz, CDCl3): δ = 7.63 (d, J = 7.6 Hz, 2H), 7.45-7.33 (m, 5H),
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7.10-7.06 (m, 2H), 6.74 (s, 1H), 2.12 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ =
169.7, 141.5, 136.8, 133.9, 130.0, 128.9, 128.6, 127.9, 124.5, 118.6, 114.2, 91.3, 82.6,
66.0, 21.0 ppm; MS (EI, 70ev) m/z (%) 291 (M+, 17.28), 255 (100); IR (neat): 3066,
2116, 1739, 1590, 1218, 1017, 952, 697 cm–1; TOF HRMS (EI) calcd. for
C17H13N3O2(M+): 291.1008; found: 291.1005.
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3-(2-azido-5-chlorophenyl)-1-phenylprop-2-yn-1-yl acetate (1h): Yield: 83% (270
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mg). Oil: H NMR (400 MHz, CDCl3): δ = 7.62-7.60 (m, 2H), 7.43-7.35 (m, 4H),
7.29-7.24 (m, 1H), 7.00 (d, J = 9.2 Hz, 1H), 6.71 (s, 1H), 2.12 (s, 3H) ppm; 13C NMR
(100 MHz, CDCl3): δ = 169.6, 140.1, 136.5, 133.4, 130.1, 129.7, 129.0, 128.7, 127.8,
119.8, 115.6, 92.5, 81.3, 65.8, 21.0 ppm; MS (EI, 70ev) m/z (%) 325 (M+, 5.83), 221
(100); IR (neat): 3064, 2127, 1738, 1571, 1297, 1097, 950, 753 cm–1; TOF HRMS (EI)
calcd. for C17H1235Cl N3O2(M+): 325.0618; found: 325.0612.
4-(2-azidophenyl)but-3-yn-2-yl methyl carbonate (1i): Yield: 88% (215 mg). Oil:
1H NMR (400 MHz, CDCl3): δ = 7.43-7.41 (m, 1H), 7.36-7.32 (m, 1H), 7.10-7.06 (m,
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2H), 5.59 (q, J = 6.8 Hz, 1H), 3.82 (s, 3H), 1.65 (d, J = 8.4 Hz, 3H) ppm; C NMR
(100 MHz, CDCl3): δ = 154.8, 141.2, 134.0, 130.0, 124.5, 118.8, 114.3, 92.5, 81.0,
64.8, 54.9, 21.3 ppm; MS (EI, 70ev) m/z (%) 245 (M+, 13.58), 130 (100); IR (neat):
2958, 2129, 1745, 1574, 1257, 1021, 939, 758 cm–1; TOF HRMS (EI) calcd. for
C12H11N3O3(M+): 245.0800; found: 245.0807.
1-(2-azidophenyl)-3-phenylprop-2-yn-1-yl methyl carbonate (3a): Yield: 79%
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(243 mg). Oil: H NMR (400 MHz, CDCl3): δ = 7.79 (d, J = 7.6 Hz, 1H), 7.48-7.41
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(m, 3H), 7.34-7.29 (m, 3H), 7.23-7.19 (m, 2H), 6.76 (s, 1H), 3.84 (s, 3H) ppm; C
NMR (100 MHz, CDCl3): δ = 154.7, 138.0, 131.9, 130.6, 129.5, 128.9, 128.3, 127.4,
125.0, 121.9, 118.3, 87.9, 84.3, 65.2, 55.1 ppm; MS (EI, 70ev) m/z (%) 307 (M+,
11.76), 204 (100); IR (neat): 2927, 1748, 1494, 1256, 1105, 948, 857, 756 cm–1; MS:
m/z (%) = 307 (M+, 4.66), 224 (100); IR (neat): 2957, 2230, 1750, 1490, 1244, 1093
cm–1; TOF HRMS (EI) calcd. for C17H13N3O3 (M+): 307.0957; found: 307.0951.
1-(2-azidophenyl)-3-(4-fluorophenyl)prop-2-yn-1-yl methyl carbonate (3c): Yield:
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72% (233 mg). Oil: H NMR (400 MHz, CDCl3): δ = 7.76 (d, J = 8.0 Hz, 1H),
7.47-7.40 (m, 3H), 7.22-7.18 (m, 2H), 7.00 (d, J = 8.8 Hz, 2H), 6.74 (s, 1H), 3.84 (s,
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3H) ppm; 13C NMR (100 MHz, CDCl3): δ = 162.8 (J = 248.5 Hz), 154.7, 138.0, 133.9
(J = 7.7 Hz), 130.6, 129.4, 127.3, 125.0, 118.3, 117.9 (J = 4.3 Hz), 115.6 (J = 21.9
Hz), 86.8, 84.1, 65.1, 55.1 ppm; MS (EI, 70ev) m/z (%) 325 (M+, 12.48), 222 (100);
IR (neat): 2957, 1750, 1443, 1244, 1157, 1092 cm–1; TOF HRMS (EI) calcd. for
C17H12FN3O3 (M+): 325.0863; found: 325.0866.
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1-(2-azidophenyl)-3-(4-(trifluoromethyl)phenyl)prop-2-yn-1-yl methyl carbonate
(3i): Yield: 69% (259 mg). Oil: 1H NMR (400 MHz, CDCl3): δ = 7.76 (d, J = 7.6 Hz,
1H), 7.57 (s, 4H), 7.43 (t, J = 7.6 Hz, 1H), 7.25-7.19 (m, 2H), 6.77 (s, 1H), 3.84 (s,
3H) ppm; 13C NMR (100 MHz, CDCl3): δ = 154.6, 138.0, 132.2, 130.8, 130.4, 129.3,
127.0, 125.7, 125.1 (q, J = 4.5 Hz), 122.4, 118.3, 86.8, 86.3, 64.9, 55.2 ppm; MS (EI,
70ev) m/z (%) 375 (M+, 18.84), 302 (100); IR (neat): 2961, 2128, 1752, 1489, 1248,
1125 cm–1; TOF HRMS (EI) calcd. for C17H12F3N3O3 (M+): 375.0831; found:
375.0836.
1-(2-azidophenyl)-3-(p-tolyl)prop-2-yn-1-yl methyl carbonate (3j): Yield: 76%
1
(244 mg). Oil: H NMR (400 MHz, CDCl3): δ = 7.78 (d, J = 7.6 Hz, 1H), 7.42-7.35
(m, 3H), 7.23-7.15 (m, 2H), 7.10 (d, J = 7.6 Hz, 2H), 6.75 (s, 1H), 3.82 (s, 3H), 2.32
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(s, 3H) ppm; C NMR (100 MHz, CDCl3): δ = 154.7, 139.1, 137.9, 131.8, 130.5,
129.5, 128.9, 127.5, 125.0, 118.7, 118.2, 88.1, 83.6, 65.2, 55.0, 21.4 ppm; MS (EI,
70ev) m/z (%) 321 (M+, 17.68), 218 (100); IR (neat): 2954, 2229, 2131, 1750, 1585,
1261 cm–1; TOF HRMS (EI) calcd. for C18H15N3O3 (M+): 321.1113; found: 321.1118.
1-(2-azidophenyl)-3-(4-chlorophenyl)prop-2-yn-1-yl methyl carbonate (3k): Yield:
1
84% (286 mg). Oil: H NMR (400 MHz, CDCl3): δ = 7.65 (d, J = 7.6 Hz, 1H),
7.31-7.26 (m, 3H), 7.16-7.04 (m, 4H), 6.64 (s, 1H), 3.71 (s, 3H) ppm; 13C NMR (100
MHz, CDCl3): δ = 154.6, 137.9, 134.9, 133.0, 130.6, 129.3, 128.5, 127.1, 124.9,
120.2, 118.2, 86.8, 85.3, 64.9, 55.0 ppm; MS (EI, 70ev) m/z (%) 341 (M+, 12.44), 219
(100); IR (neat): 2959, 2126, 1750, 1488, 1244, 1013 cm–1; TOF HRMS (EI) calcd.
for C17H1235ClN3O3 (M+): 341.0567; found: 341.0561.
Procedure for Synthesis of 2a−k: Typical Procedure for preparation of
(2-Phenylquinolin-4-yl) methyl carbonate (2a)
Typical Procedure Ι: To a dried Schlenk tube were added AgClO4 (3.1 mg, 0.015
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mmol), Au(PPh3)Cl (7.6 mg, 0.015 mmol), and DCE (1 mL) sequentially under a
nitrogen atmosphere at room temperature. The resulting mixture was stirred at room
temperature for about 10 min, which was followed by the addition of 1a (92.1 mg,
0.30 mmol) and 2 mL of DCE. The resulting mixture was then submerged in an oil
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bath preheated to 60 C. After complete consumption of the starting material as
monitored by TLC, the mixture was transferred with 30 mL of Et2O and concentrated
under reduced pressure. The residue was purified by chromatography on silica gel
(eluent: petroleum ether/ethyl acetate = 10/1) to afford 2a (37.7 mg, 45%): solid; m.p.
142-146 oC (petroleum ether /CHCl3); 1H NMR (400 MHz, CDCl3): δ = 8.21-8.18 (d,
J = 8.8 Hz, 1H), 8.16-8.14 (d, J = 7.6 Hz, 2H), 8.03 (d, J = 8.8 Hz, 1H), 7.89 (s, 1H),
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7.76 (t, J = 7.6 Hz, 1H), 7.58-7.47 (m, 4H), 4.01 (s, 3H) ppm; C NMR (100 MHz,
CDCl3): δ = 158.3, 154.8, 153.0, 149.9, 139.1, 130.4, 129.8, 129.7, 128.8, 127.6,
126.7, 120.9, 120.8, 109.8, 55.9 ppm; MS (EI, 70ev) m/z (%) 279 (M+, 100); IR (neat):
2936, 1771, 1491, 1244, 1154 cm–1; TOF HRMS (EI) calcd. for C17H13NO3 (M+):
279.0895; found: 279.0899.
2-(4-Bromophenyl)quinolin-4-yl methyl carbonate (2b)
The reaction of 1b (115.5 mg, 0.30 mmol) catalyzed by AgClO4 (3.1 mg, 0.015 mmol)
and Au(PPh3)Cl (7.6 mg, 0.015 mmol) in 3 mL of DCE afforded 2b (54.6 mg, 51%)
(eluent: petroleum ether/ethyl acetate = 20/1): solid; m.p. 132-136 oC (petroleum ether
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/CHCl3); H NMR (400 MHz, CDCl3): δ = 8.16 (d, J = 8.8 Hz, 1H), 8.03 (d, J = 8.8
Hz, 3H), 7.85 (s, 1H), 7.76 (t, J = 7.8 Hz, 1H), 7.64 (d, J = 8.4 Hz, 2H), 7.56 (t, J =
7.6 Hz, 1H), 4.01 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ = 156.9, 154.9, 153.0,
149.8, 137.9, 132.0, 130.5, 129.7, 129.0, 126.9, 124.3, 120.9, 120.8, 109.3, 55.9 ppm;
MS (EI, 70ev) m/z (%) 359 (M+(81Br), 99), 357 (M+(79Br), 100); IR (neat): 2923,
2203, 2117, 1720, 1629, 1598, 1567, 1397, 912 cm–1; TOF HRMS (EI) calcd. for
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C17H12NO3 Br (M+): 357.0001; found: 356.9996.
2-(4-Fluorophenyl)quinolin-4-yl methyl carbonate (2c)
The reaction of 1c (97.5 mg, 0.30 mmol) catalyzed by AgClO4 (3.1 mg, 0.015 mmol)
and Au(PPh3)Cl (7.6 mg, 0.015 mmol) in 3 mL of DCE afforded 2c (42.8 mg, 48%)
(eluent: petroleum ether/ethyl acetate = 10/1): solid; m.p. 151-154 oC (petroleum ether
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/CHCl3); H NMR (400 MHz, CDCl3): δ = 8.18-8.12 (m, 3H), 8.02 (d, J = 8.8 Hz,
1H), 7.84 (s, 1H), 7.76 (t, J = 7.6 Hz, 1H), 7.57 (t, J = 7.2 Hz, 1H), 7.20 (t, J = 8.4 Hz,
2H), 4.01 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ = 164.0 (J = 247.7 Hz), 157.1,
154.9, 153.0, 149.8, 135.2 (J = 2.9 Hz), 130.5, 129.6, 129.5 (J = 9.2 Hz), 126.7, 120.9,
120.6, 115.8 (J = 21.1 Hz), 109.4, 55.9 ppm; MS (EI, 70ev) m/z (%) 297 (M+, 100);
IR (neat): 2983, 1548, 1406, 1250, 1052 cm–1; TOF HRMS (EI) calcd. for
C17H12NO3F (M+): 297.0801; found: 297.0807.
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2-(2-Bromophenyl)quinolin-4-yl methyl carbonate (2d)
The reaction of 1d (116.2 mg, 0.30 mmol) catalyzed by AgClO4 (3.1 mg, 0.015 mmol)
and Au(PPh3)Cl (7.6 mg, 0.015 mmol) in 3 mL of DCE afforded 2d (50.3 mg, 47%)
(eluent: petroleum ether/ethyl acetate = 20/1): solid; m.p. 146-149 oC (petroleum ether
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/CHCl3); H NMR (400 MHz, CDCl3): δ = 8.20 (d, J = 8.8 Hz, 1H), 8.09 (d, J = 8.8
Hz, 1H), 7.80-7.60 (m, 5H), 7.47-7.43 (m, 1H), 7.32 (t, J = 7.6 Hz, 1H), 4.00 (s, 3H)
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ppm; C NMR (100 MHz, CDCl3): δ = 159.4, 153.6, 152.9, 149.5, 141.0, 133.3,
131.6, 130.4, 130.2, 129.7, 127.7, 127.2, 121.7, 121.0, 120.8, 113.6, 55.9 ppm; MS
(EI, 70ev) m/z (%) 359 (M+(81Br), 12.30), 357 (M+(79Br), 12.20) , 105 (100); IR (neat):
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2973, 1766, 1474, 1253, 1153 cm–1; TOF HRMS (EI) calcd. for C17H12NO3 Br (M+):
357.0001; found: 357.0010.
(6-Methyl-2-phenylquinolin-4-yl) methyl carbonate (2e)
The reaction of 1e (96.3 mg, 0.30 mmol) catalyzed by AgClO4 (3.1 mg, 0.015 mmol)
and Au(PPh3)Cl (7.6 mg, 0.015 mmol) in 3 mL of DCE afforded 2e (33.4 mg, 38%)
(eluent: petroleum ether/ethyl acetate = 10/1): solid; m.p. 148-152 oC (petroleum ether
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/CHCl3); H NMR (400 MHz, CDCl3): δ = 8.14-8.07 (m, 3H), 7.83 (s, 1H), 7.77 (s,
1H), 7.58 (d, J = 9.2 Hz, 1H), 7.51-7.43 (m, 3H), 4.01 (s, 3H), 2.55 (s, 3H) ppm; 13C
NMR (100 MHz, CDCl3): δ = 157.3, 154.2, 153.1, 148.6, 139.2, 136.9, 132.7, 129.4,
128.8, 127.4, 120.7, 119.6, 109.9, 55.9, 21.8 ppm; MS (EI, 70ev) m/z (%) 293 (M+,
100) ; IR (neat): 2980, 1770, 1494, 1251, 1152 cm–1; TOF HRMS (EI) calcd. for
C18H15NO3 (M+): 293.1052; found: 293.1057.
6-Chloro-2-phenylquinolin-4-yl methyl carbonate (2f)
The reaction of 1f (102.3 mg, 0.30 mmol) catalyzed by AgClO4 (3.1 mg, 0.015 mmol)
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and Au(PPh3)Cl (7.6 mg, 0.015 mmol) in 3 mL of DCE afforded 2f (38.5 mg, 41%)
(eluent: petroleum ether/ethyl acetate = 20/1): solid; m.p. 128-132 oC (petroleum ether
/CHCl3); 1H NMR (400 MHz, CDCl3): δ = 8.14-8.11 (m, 3H), 8.02-8.01 (m, 1H), 7.93
(s, 1H), 7.69 (dd, J1 = 8.8 Hz, J2 = 2.2 Hz, 1H), 7.53-7.48 (m, 3H), 4.03 (s, 3H) ppm;
13C NMR (100 MHz, CDCl3): δ = 158.5, 153.9, 152.8, 148.2, 138.7, 132.7, 131.35,
131.33, 129.9, 128.9, 127.5, 121.4, 120.1, 110.4, 56.1 ppm; MS (EI, 70ev) m/z (%)
315 (M+(37Cl), 35.40), 313 (M+(35Cl), 100); IR (neat): 2957, 1769, 1486, 1247, 1116
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cm–1; TOF HRMS (EI) calcd. for C17H12NO3 Cl (M+): 313.0506; found: 313.0511.
2-Phenylquinolin-4-yl acetate (2g)
The reaction of 1g (87.3 mg, 0.30 mmol) catalyzed by AgClO4 (3.1 mg, 0.015 mmol)
and Au(PPh3)Cl (7.6 mg, 0.015 mmol) in 3 mL of DCE afforded 2g (41.0 mg, 52%)
1
(eluent: petroleum ether/ethyl acetate = 10/1): oil; H NMR (400 MHz, CDCl3): δ =
8.20-8.13 (m, 3H), 7.92 (d, J = 8.8 Hz, 1H), 7.77-7.75 (m, 2H), 7.54-7.48 (m, 4H),
2.51 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ = 168.2, 158.3, 154.7, 150.0, 139.2,
130.2, 129.9, 129.6, 128.8, 127.6, 126.6, 121.2, 121.0, 110.9, 21.2 ppm; MS (EI, 70ev)
m/z (%) 263 (M+, 25.00), 221 (100); IR (neat): 2925, 1773, 1499, 1254, 1142 cm–1;
TOF HRMS (EI) calcd. for C17H13NO2 (M+): 263.0946; found: 263.0949.
6-Chloro-2-phenylquinolin-4-yl acetate (2h)
The reaction of 1h (97.5 mg, 0.30 mmol) catalyzed by AgClO4 (3.1 mg, 0.015 mmol)
and Au(PPh3)Cl (7.6 mg, 0.015 mmol) in 3 mL of DCE afforded 2h (49.1 mg, 55%)
1
(eluent: petroleum ether/ethyl acetate = 30/1): oil; H NMR (400 MHz, CDCl3): δ =
8.17-8.12 (m, 3H), 7.92 (d, J = 2.4 Hz, 1H), 7.83(s, 1H), 7.70 (dd, J1 = 8.8 Hz, J2 =
2.0 Hz, 1H), 7.57-7.47 (m, 3H), 2.54 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ =
168.0, 158.5, 153.7, 148.3, 138.8, 132.5, 131.5, 131.2, 129.8, 128.9, 127.5, 121.8,
120.1, 111.5, 21.2 ppm; MS (EI, 70ev) m/z (%) 299 (M+(37Cl), 8.52), 297 (M+(35Cl),
25.00), 255 (100); IR (neat): 2959, 1763, 1496, 1257, 1196 cm–1; TOF HRMS (EI)
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calcd. for C17H12NO2 Cl (M+): 297.0557; found: 297.0554.
(2-Phenylquinolin-4-yl) methyl carbonate (2a)
Typical Procedure : To a dried Schlenk tube were added AgOTf (9.3 mg, 0.030
mmol), Au(PPh3)Cl (15.2 mg, 0.030 mmol), and DCE (1 mL) sequentially under a
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nitrogen atmosphere at room temperature. The resulting mixture was stirred at room
temperature for about 10 min, which was followed by the addition of 3a (92.4 mg,
0.30 mmol) and 2 mL of DCE. After complete consumption of the starting material as
monitored by TLC, the mixture was transferred with 30 mL of Et2O and concentrated
under reduced pressure. The residue was purified by chromatography on silica gel
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(eluent: petroleum ether/ethyl acetate = 10/1) to afford 2a (46.1 mg, 55%): H NMR
(400 MHz, CDCl3): δ = 8.21-8.18 (d, J = 8.8 Hz, 1H), δ = 8.16-8.14 (d, J = 7.6 Hz,
2H), 8.03 (d, J = 8.8 Hz, 1H), 7.89 (s, 1H), 7.76 (t, J = 8.0 Hz, 1H), 7.58-7.47 (m, 4H),
4.01 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ = 158.3, 154.8, 153.0, 149.9, 139.1,
130.4, 129.8, 129.7, 128.8, 127.6, 126.7, 120.9, 120.8, 109.8, 55.9 ppm.
2-(4-Fluorophenyl)quinolin-4-yl methyl carbonate (2c)
The reaction of 3c (97.5 mg, 0.30 mmol) catalyzed by AgOTf (9.3 mg, 0.030 mmol)
and Au(PPh3)Cl (15.2 mg, 0.030 mmol) in 3 mL of DCE afforded 2c (47.3 mg, 53%)
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(eluent: petroleum ether/ethyl acetate = 20/1): H NMR (400 MHz, CDCl3): δ =
8.18-8.12 (m, 3H), 8.02 (d, J = 8.8 Hz, 1H), 7.84 (s, 1H), 7.76 (t, J = 7.2 Hz, 1H),
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7.57 (t, J = 7.2 Hz, 1H), 7.22-7.18 (m, 2H), 4.01 (s, 3H) ppm; C NMR (100 MHz,
CDCl3): δ = 164.0 (J = 247.7 Hz), 157.1, 154.9, 153.0, 149.8, 135.2 (J = 2.9 Hz),
130.5, 129.6, 129.5 (J = 9.2 Hz), 126.7, 120.9, 120.6, 115.8 (J = 21.1 Hz), 109.4, 55.9
ppm.
(2-(4-(Trifluoromethyl)phenyl)quinolin-4-yl) methyl carbonate (2i)
The reaction of 3i (112.5 mg, 0.30 mmol) catalyzed by AgOTf (9.3 mg, 0.030 mmol)
and Au(PPh3)Cl (15.2 mg, 0.030 mmol) in 3 mL of DCE afforded 2i (52.1 mg, 51%)
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(eluent: petroleum ether/ethyl acetate = 20/1): oil; H NMR (400 MHz, CDCl3): δ =
8.26 (d, J = 8.0 Hz, 1H), 8.19 (d, J = 8.8 Hz, 1H), 8.05 (d, J = 8.4 Hz, 1H), 7.91 (s,
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1H), 7.80-7.76 (m, 3H), 7.59 (t, J = 7.6 Hz, 1H), 4.02 (s, 3H) ppm; C NMR (100
MHz, CDCl3): δ = 156.5, 155.0, 153.0, 149.9, 142.3, 130.7, 129.9, 127.8, 127.2,
125.7 (q, J = 2.5 Hz), 121.0, 109.6, 56.0 ppm; MS (EI, 70ev) m/z (%) 347 (M+, 100);
IR (neat): 2966, 1769, 1442, 1322, 1238, 1162 cm–1; TOF HRMS (EI) calcd. for
C17H12NO3CF3 (M+): 347.0769; found: 347.0772.
(2-(P-tolyl)quinolin-4-yl) methyl carbonate (2j)
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The reaction of 3j (96.3 mg, 0.30 mmol) catalyzed by AgOTf (9.3 mg, 0.030 mmol)
and Au(PPh3)Cl (15.2 mg, 0.030 mmol) in 3 mL of DCE afforded 2j (46.6 mg, 53%)
(eluent: petroleum ether/ethyl acetate = 30/1): solid; m.p. 115-119 oC (petroleum ether
1
/CHCl3); H NMR (400 MHz, CDCl3): δ = 8.17 (d, J = 8.8 Hz, 1H), 8.06-8.00 (m,
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3H), 7.86 (s, 1H), 7.74 (t, J = 7.4 Hz, 1H), 7.53 (t, J = 7.6 Hz, 1H), 7.32 (d, J = 8.0 Hz,
13
2H), 4.00 (s, 3H), 2.42 (s, 3H) ppm; C NMR (100 MHz, CDCl3): δ = 158.2, 154.7,
153.1, 149.9, 139.8, 136.3, 130.3, 129.7, 129.6, 127.4, 126.5, 120.8, 120.7, 109.6,
55.9, 21.3 ppm; MS (EI, 70ev) m/z (%) 293 (M+, 100); IR (neat): 1766, 1606, 1503,
1430, 1254, 1009 cm–1; TOF HRMS (EI) calcd. for C18H15NO3 (M+): 293.1052; found:
293.1051.
2-(4-Chlorophenyl)quinolin-4-yl methyl carbonate (2k)
The reaction of 3k (102.3 mg, 0.30 mmol) catalyzed by AgOTf (9.3 mg, 0.030 mmol)
and Au(PPh3)Cl (15.2 mg, 0.030 mmol) in 3 mL of DCE afforded 2k (45.1 mg, 48%)
(eluent: petroleum ether/ethyl acetate = 20/1): solid; m.p. 126-130 oC (petroleum ether
1
/CHCl3); H NMR (400 MHz, CDCl3): δ = 8.17 (d, J = 8.4 Hz, 1H), 8.10 (d, J = 8.8
Hz, 2H), 8.03 (d, J = 8.2 Hz, 1H), 7.86 (s, 1H), 7.77 (t, J = 7.6 Hz, 1H), 7.57 (t, J =
7.8 Hz, 1H), 7.49 (d, J = 8.8 Hz, 2H), 4.02 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3):
δ = 156.9, 154.9, 153.0, 149.9, 137.5, 135.9, 130.5, 129.7, 129.0, 128.8, 126.9, 120.9,
120.8, 109.4, 56.0 ppm; MS (EI, 70ev) m/z (%) 315 (M+(37Cl), 34.50), 313 (M+(35Cl),
100); IR (neat): 3053, 1769, 1438, 1270, 1089, 1013 cm–1; TOF HRMS (EI) calcd. for
35
C17H12NO3 Cl (M+): 313.0506; found: 313.0504.
Procedure for preparation of
1-Azido-2-(3-methoxy-3-phenylprop-1-yn-1-yl)benzene (5a)
To a dried Schlenk tube were added AgSbF6 (5.2 mg, 0.015 mmol), Au(PPh3)Cl (7.6
mg, 0.015 mmol), and DCE (1 mL) sequentially under a nitrogen atmosphere at room
temperature. The resulting mixture was stirred at room temperature for about 10 min,
which was followed by the addition of 1a (93.1 mg, 0.30 mmol) and 2 mL of THF.
o
The resulting mixture was then submerged in an oil bath preheated to 60 C. After
complete consumption of the starting material as monitored by TLC, the mixture was
transferred with 30 mL of Et2O and concentrated under reduced pressure. The residue
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was purified by chromatography on silica gel (eluent: petroleum ether/ethyl acetate =
1
20/1) to afford 5a (59.2 mg, 75%): oil H NMR (400 MHz, CDCl3): δ = 7.60 (d, J =
7
7.2 Hz, 2H), 7.46-7.30 (m, 5H), 7.12-7.04 (m, 2H), 5.36 (s, 1H), 3.51 (s, 3H) ppm;
13C NMR (100 MHz, CDCl3): δ = 141.3, 138.2, 133.7, 129.7, 128.5, 128.4, 127.5,
124.5, 118.5, 114.6, 92.5, 83.3, 73.5, 55.9 ppm; MS (EI, 70ev) m/z (%) 263 (M+, 15) ,
79 (100); IR (neat): 2932, 2126, 2101, 1720, 1597, 1487, 1447, 1279, 1189, 1075
cm–1; TOF HRMS (EI) calcd. for C16H13N3O (M+): 263.1059; found: 263.1052.
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AUTHOR INFORMATION
Corresponding Author
*E-mail: wululing@zju.edu.cn
§ Prof. Xian Huang passed away on March 6, 2010. He had been fully in charge of this
project. At this moment, Prof. Luling Wu is helping him to finish all the projects with
the help from Prof. Shengming Ma.
ACKNOWLEDGMENT
We are grateful to the National Natural Science Foundation of China (Project Nos.
20872127 and J0830431) and National Basic Research Program of China (973
Program, 2009CB825300) and CAS Academician Foundation of Zhejiang Province
and the Fundamental Research Funds for the Central Universities for financial
support.
1
Supporting Information. Figures 1 and 2, copies of H and 13C NMR spectra for
compounds 1, 2, and 3 and CIF files for 2c, and 4c. This material is available free of
charge via the Internet at http://pubs.acs.org.
REFERENCES
(1) C X–ray crystal data for 2c: C17H12NO3F; M= 297.28; crystal system: monoclinic;
space group: C 2/c; final R indices (I > 2σ(I)) R1= 0.0404, wR2= 0.0737, R indices
(all data) R1= 0.0634, wR2= 0.0843; a=3.8270(4) Å, b=19.9545(12) Å, c=8.9557(6)
Å; α=90.00, β= 90.076, γ=90.00, V= 683.86(9) Å3, T=293(2) K, Z= 2; reflections
collected/unique: 4885/2466 (R(int)= 0.0314); number of observations ( > 2σ(I)):
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1884; parameters: 200. Supplementary crystallographic data have been deposited at
the Cambridge Crystallographic Data Centre, CCDC 886294.
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(2) C X–ray crystal data for 4c: C15H10NOF; M= 239.24; crystal system: monoclinic;
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(all data) R1= 0.0420, wR2= 0.0968; a=11.7400(5) Å, b=7.1758(3) Å, c=13.2748(7)
Å; α=90.00, β= 92.215(4), γ=90.00, V= 1117.49(9) Å3, T=293(2) K, Z= 4; reflections
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1738; parameters: 164. Supplementary crystallographic data have been deposited at
the Cambridge Crystallographic Data Centre, CCDC 886297.
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