The photochemical synthesis of N-arylacetyl lactams

Article abstract of DOI:10.3184/174751913X13594855388300

The photochemical formation is described of N-arylacetyl lactams from the corresponding N-phenylglyoxylic acid derivatives of pyrrolidine and piperidine-2-carboxylic acids in an acetone:water mixture containing potassium carbonate. Evidence is presented f

Full text of DOI:10.3184/174751913X13594855388300

JOURNAL OF CHEMICAL RESEARCH 2013
RESEARCH PAPER 143
MARCH, 143–145
The photochemical synthesis of N-arylacetyl lactams
Lei Jiang, Nan Ma, Jun Qiu and Ronghua Zhang*
Department of Chemistry, Tongji University, Shanghai 200092, P. R. China
The photochemical formation is described of N-arylacetyl lactams from the corresponding N-phenylglyoxylic acid
derivatives of pyrrolidine and piperidine-2-carboxylic acids in an acetone:water mixture containing potassium car-
bonate. Evidence is presented for the possible formation and cleavage of a cyclic ether during this process which
leads to the 1, 4-transfer of a carbonyl group.
Keywords: photo-catalysis, N-arylacetyl lactams, cyclisation, ring-opening, acetone
N-Arylacetyl lactams belong to the family of N-acetyl lactams
that have a wide range of biological activity.1–3 They are used
in the manufacture of health foods and pharmaceuticals.4 Many
methods for the preparation of N-arylacetyl lactams have been
reported.5–8 Of these, the reaction of arylacetyl halides with
lactim ethers or N-trimethylsilyl lactams has been the most
widely used. However, photochemical reactions as a novel
method for the preparation of N-arylacetyl lactams has not
been reported. Photoreactions generally serve as an environ-
mental friendly alternative to the traditional methods.
main products 2a and 5. As shown in Table 3, the yield of 2a
depended on the corresponding reaction time. Following the
photo-catalysis study of 1a, compound 5 was converted into 2a
Table 1 Synthesis and photoreaction of phenylglyoxamide
derivativesa
In view of this, we report an efficient and novel photochem-
ical method for the synthesis of N-arylacetyl lactams. In the
past, photochemical reactions involving the intramolecular
reaction of phenylglyoxylamides and their derivatives, gener-
ally gave only cyclisation products.9–12 For example, Wang
developed a regioselective method for β-lactam formation and
gained information about the mechanism of this process by
studying photochemical properties of N-trimethylsilylmethyl-
and N-tributylstannylmethyl-substituted α-ketoamides.9 In
contrast to the common cyclisation product, several benzoyl-
formamides of α-amino acid gave the corresponding N-
arylacetyl lactams by photo-catalysis in our study. In this
photo-catalysed reaction, the ring-opening process may occur
by attack of singlet acetone on benzyl carbon.
Entry
1b
Substrate
Product
Yield/%c
64
2
20
3
4
5
6
7
46
52
Results and discussion
The photoreaction of 1a was conducted with potassium
carbonate as a base in a mixed acetone–water solvent and irra-
diating with 500 W medium-pressure mercury lamp for 48 h.
The product 2a was isolated in 64% yield (Entry 1). The
4-methoxy substituent was introduced to 1a for the purpose
of investigating the effect of substituent on the outcome of
the photoreaction. Using 1b as a substrate, we obtained the
compound 3 rather than 2b as anticipated (Scheme 1). The
formation of 3 may be due to attack of acetone on the benzyl
carbon. In further study, photoreaction on the substrate 1c
whose structure was very similar with that of 1a gave the
expected product 2c. Fortunately, in the presence of 4-methoxy
or 2-methoxy substituent on 1a, the corresponding products 2d
or 2e were observed. On the other hand, in order to explore the
effect of amino acids structure in substrates, 1f and 1g in which
there were noncyclic amino acids structure comparing with 1a
and 1c were synthesised. With 1f and 1g as substrates, we did
not obtain the expected products comparable to 1a (Table 1),
i.e. the cyclic amino acid structure was a crucial part of the
substrates.
57
24
NDd
ND
a Standard conditions: K2CO3 (0.4 mmol), acetone (100 mL),
H2O (8 mL), 1b–g (1 mmol), 500W medium- pressure mercury
lamp for 8 h under N2, 25 °C; b 48 h; c isolated yield; d ND, not
determined.
Table 2 Effect of solvent on photoreaction of 1aa
It was interesting to note that photo-irradiation of 1a led to
2a or the 5 in different solvents. In acetonitrile, methanol or
DCM with water, 5 was formed as the major product without
any 2a (Table 2). In contrast, photoreactions that were con-
ducted with 1a in mixed solvent of acetone and water gave two
Substrate
Solvent
Product Yield/% Conversion/%
1a
1a
1a
1a
acetone/H2O
MeOH/ H2O
CH3CN/ H2O
CH2Cl2/ H2O
5,2a
34,20
56
60
55
76
51
5
5
5
78
47
* Correspondent. E-mail: rhzhang@tongji.edu.cn
a Standard conditions except for solvent.

144 JOURNAL OF CHEMICAL RESEARCH 2013
Chemical shifts were reported in ppm. Mass spectra were obtained
using Finnign MAT 212 and HRMS were obtained using Agilent
QTOF 6210. All reactions were performed in a photochemical reactor
(XPA, 500W medium-pressure mercury lamp, Nanjing Xujiang
Electrical Machinery Co. Ltd, Nanjing, China).
Synthesis of N-(2-oxo-2-phenylacetyl)-α-amino acid (1a–g); general
procedure
Method A: Potassium hydroxide (1.80 g, 32 mmol), water (160.0 mL),
acetophenone (18.02 g, 150 mmol) and potassium permanganate
(24.97 g, 158 mmol) in portions were added to a 250 mL round bottom
flask equipped with a magnetic stir bar with batching.21 After the reac-
tion completed (monitored by TLC analysis), sodium bisulfate was
added to the mixture until colour turned grey. Then, the black manga-
nese dioxide solid was removed by filtering. The pH of solution was
adjusted to 3–4 with dilute hydrochloric acid. Byproduct benzoate and
the unchanged acetophenone were removed by extraction with ethyl
acetate. When pH of solution was 1–2, the water solution was extracted
with ethyl acetate and the combined organic layer was dried with
anhydrous sodium sulfate. Removal of the solvent in vacuo yielded
benzoylformic acid as pale-yellow solid.
Method B: Benzoylformic acid (2.25 g, 15 mmol), triethylamine
(1.82 g, 18 mmol), dichloromethane (20.0 mL) and thionyl chloride
(4.4 mL, 60 mmol) were added dropwise to a dried 100 mL round
bottom flask equipped with a magnetic stir bar. After 0.5 h at 0 °C, the
reaction stirred for 6 h at room temperature. The solvent and excessive
thionyl chloride were removed in vacuo. The residue was diluted
with dichloromethane (5.0 mL) and added to solution of proline
(1.73 g, 15 mmol) and triethylamine (1.82 g, 15 mmol) in dichloro-
methane (20.0 mL) at 0 °C. The reaction was stirred overnight. The
solution was washed with dilute hydrochloric acid solution and dried
over anhydrous sodium sulfate. The solvent was removed by rotary
evaporation and the residue was purified by column chromatography
on silica gel (petroleum/ethyl acetate = 4/1). Removal of the solvent
gave 1a.
Scheme 1 Photoreaction outcome of 1b.
Scheme 2 Direct transformation of 5 into 2a.
Table 3 Effect of irradiation time on yields of 2a and 5a
Time/h
Yield/%
5
2a
4
8
12
24
48
34
24
20
36
43
56
64
20
n.d.
n.d
a Conditions: K2CO3 (0.4 mmol), acetone (100 mL), H2O (8 mL),
1a (1 mmol), 500W medium-pressure mercury lamp, N2.
directly under the same condition (Scheme 2). This provided
evidence for the existence of photo-catalysed ring-opening
process. The mechanism9,12 for cyclisation concerning Type II
photoreaction of benzoylformamides had already been
reported. In fact, photochemical studies on pyranocoumarin
rearrangements13 by Li and co-workers led to the observation
of ring-opening process upon UV irradiation. It had been
reported that acetone played a very important role in photo-
chemistry.14–16
Most investigators interpreted that carbon oxygen single
bond could form between acetone and electron-deficient
double bonds and subsequently acetone recovered as a result
of the cleavage of C–O bond in the photo-catalysis process.17–20
The benzyl carbon in component 5 is electron-deficient with
the interaction of carbonyl and the oxygen atom. Based on
these facts, we speculate here that the conversion of 5 into 2a
presumably involved in the photo-catalysed ring-opening
process by attack of singlet acetone on benzyl carbon and
subsequently the acetone is regenerated by photolytic cleavage
of the C–O bond.
Photochemical reaction; general procedure
In quartz tube made of silica, a solution of 1a (0.5 mmol) and potas-
sium carbonate (27 mg, 0.2 mmol) in acetone/water (100 mL/6 mL)
was stirred with irradiation of 500W medium-pressure mercury lamp
cooled by two water cooling jackets at 25 °C under nitrogen. After
removal of acetone in vacuo, the residual solution was extracted with
ethyl acetate. The organic layer was dried over anhydrous sodium
sulfate and ethyl acetate was removed in vacuo. The oil liquid was
purified by preparative thin layer chromatography with 10% ethyl
acetate–90% petroleum ether as the mobile phase and gave 2a.
(Earlier reports of compound 1a, 1c, 1f, 2c, 2d, 3 exist in which no
spectroscopic data are given.)
1-(2-Oxo-2-phenylacetyl)pyrrolidine-2-carboxylic acid (1a): Pale-
yellow solid, m.p. 126–128 °C; IR (cm−1): 3548, 3474, 3413, 3237,
1
1639, 1620, 617, 473; H NMR (CD3Cl, 3:1 mixture of trans–cis
amide rotamers, data for major rotamer): δ 10.01 (s, 1H, –COOH),
8.06(d, J = 7.6 Hz, 2H, ArH), 7.64 (t, J = 7.6 Hz, 1H, ArH), 7.51 (t,
J = 8.0 Hz, 2H, ArH), 4.71 (dd, J = 4.0, 8.4 Hz, 1H, –NCH), 3.58 (m,
1H, –NCH2), 3.50 (m, 1H, –NCH2), 2.31 (m, 1H, –CH2), 2.16 (m, 1H,
–CH2), 1.97 (m, 2H, –CH2); 13C NMR: δ 190.8, 175.2, 165.6, 134.9,
132.6, 130.1, 129.1, 58.4, 47.3, 28.9, 24.6; ESI-MS m/z: 270.07
[M+Na]+.
1-[2-(4-Methoxyphenyl)-2-oxoacetyl]pyrrolidine-2-carboxylicacid
(1b): Pale-yellow solid, m.p. 84–86 °C; IR (cm−1): 3548, 3474, 3413,
3240, 1642, 1620, 617, 480; 1H NMR (CD3Cl, 3:1 mixture of trans–
cis amide rotamers, data for major rotamer): δ 9.26 (s, 1H, –COOH),
8.03 (d, J = 8.8 Hz, 2H, ArH), 6.99 (d, J = 8.8 Hz, 2H, ArH), 4.70 (dd,
J = 4.0, 8.8 Hz, 1H, –NCH), 3.88 (s, 3H, –OCH3), 3.59 (m, 1H,
–NCH2), 3.50 (m, 1H, –NCH2), 2.31 (m, 1H, –CH2), 2.19 (m, 1H,
–CH2), 2.00 (m, 2H, –CH2); 13C NMR: δ 207.4, 189.4, 166.1, 165.1,
132.6, 125.8, 114.5, 58.5, 55.7, 47.4, 28.9, 24.7; ESI-MS m/z: 300.13
[M+Na]+; HR-MS (ESI) m/z: Calcd for C14H15NO5: 300.0848, found
300.0847 [M+Na]+.
Conclusions
In summary, we have demonstrated that N-arylacetyl lactams
2a and 2c–e could be photochemically generated from stable
photoprecursors by a single step. Moreover, the N-arylacetyl
lactams as 1, 4-carbonyl transfer products were achieved via
photo-catalysis for cyclisation and ring-opening. Further
experiments to develop a plausible mechanism for the photo-
catalytic ring-opening are in progress.
1-(2-Oxo-2-phenylacetyl)piperidine-2-carboxylic acid (1c): Pale-
yellow solid, m.p. 216.4–217.3 °C; IR (cm−1): 3545, 3474, 3417, 3234,
1639, 1617, 739, 617, 473; 1H NMR (CD3Cl, 4:1 mixture of trans–cis
amide rotamers, data for major rotamer): δ 10.30 (s, 1H, –COOH),
8.02(d, J = 7.6 Hz, 2H, ArH), 7.64 (t, J = 7.6 Hz, 1H, ArH), 7.51 (t,
J = 7.6 Hz, 2H, ArH), 5.44 (d, J = 4.8 Hz, 1H, –NCH), 3.50 (d,
Experimental
Melting points were taken on WRS-2A micro melting point apparatus
and the thermometer was uncorrected. IR spectra were obtained on
Nicolet FT-IR using KBr disks. 1H NMR and 13C NMR spectra were
recorded with Bruker ARX 400 using TMS as internal standard.

JOURNAL OF CHEMICAL RESEARCH 2013 145
J = 13.2 Hz, 1H, –NCH2), 3.24 (td, J = 13.2 Hz, 1H, –NCH2), 2.39 (d,
J = 13.2 Hz, 1H, –CH2), 1.79 (m, 1H, –CH2), 1.4–1.7 (m, 4H,
–CH2CH2); 13C NMR: δ 191.2, 179.0, 167.2, 134.8, 133.0, 129.8,
129.1, 52.9, 44.4, 26.5, 25.1, 20.9; ESI-MS m/z: 284.10 [M+Na]+.
1-[2-(4-Methoxyphenyl)-2-oxoacetyl]piperidine-2-carboxylic acid
(1d): Pale-yellow solid, m.p. 136.6–138.3 °C; IR (cm−1): 3545, 3471,
2-Hydroxy-1-(4-methoxyphenyl)pent-2-ene-1,4-dione (3): Orange
1
oil, IR (cm−1): 3548, 3474, 3413, 3237, 1642, 1620, 620, 476; H
NMR (CDCl3): δ 16.33 (s, 1H, –OH), 7.89 (d, J = 8.8 Hz, 2H, ArH),
6.97 (d, J = 8.8 Hz, 2H, ArH), 6.14 (s, 1H, –C=CHCO), 3.89 (s, 3H,
–OCH3), 2.19 (s, 3H, –COCH3); 13C NMR: δ 191.6, 184.2, 163.1,
131.2, 129.1, 127.5, 113.9, 95.8, 55. 5, 25.2; HR-MS (API) m/z: Calcd
for C11H13O3:193.0865, found 193.0866 [M]+.
1
3413, 3240, 1636, 1620, 611, 476; H NMR (CD3Cl, 4:1 mixture
of trans–cis amide rotamers, data for major rotamer): δ 8.69 (s, 1H,
–COOH), 8.01 (d, J = 8.8 Hz, 2H, ArH), 7.01 (d, J = 8.8 Hz, 2H, ArH),
5.47 (d, J = 4.8 Hz, 1H, –NCH), 3.90 (s, 3H, –OCH3), 3.54 (d, J =
13.6 Hz, 1H, –CH2), 3.25 (td, J = 13.6 Hz, 1H, –CH2), 2.42 (d, J =
13.2 Hz, 1H, –CH2), 1.82 (m, 1H, –CH2), 1.4–1.7 (m, 4H, –CH2CH2);
13C NMR: δ 190.1, 175.3, 167.9, 165.1, 132.3, 126.1, 114.5, 55.7,
51.4, 44.4, 26.2, 24.8, 21.1; ESI-MS m/z: 314.15 [M+Na]+; HR-MS
(ESI) m/z: Calcd for C15H17 NO5:314.1004, found 314.1003
[M+Na]+.
2-Hydroxy-2-phenyl-N-styrylacetamide (4): Pale-yellow oil, IR
(cm−1): 3548, 3474, 3413, 3234, 1639, 1617, 617, 473; 1H NMR
(CDCl3): δ 9.68 (d, J = 10 Hz, 1H, –NH), 7.74 (m, J = 8.0 Hz, 2H,
ArH), 7.38 (m, 5H, ArH), 7.30 (m, 3H, ArH), 6.96 (dd, J = 9.6,
11.2 Hz, 1H, –HC=CH), 5.85 (d, J = 9.6 Hz, 1H, -HC=CH), 4.23 (s,
1H, –OH), 2.47 (s, 1H, –CH(OH)Ar); 13C NMR: δ 171.4, 138.4, 135.4,
128.0, 127.9, 127.0, 126.8, 121.1, 111.9, 81.1, 76.0; ESI-MS m/z:
252.08 [M]−; HR-MS (ESI) m/z: Calcd for C16H15NO2:252.1025,
found 252. 1023 [M]−.
2-Phenyltetrahydropyrrolo[2,1-b]oxazol-3(2H)-one (5): Pale-yellow
oil (two diastereoisomer, isolated by TLC); IR (cm−1,the mixture):
2979, 2945, 2894, 1719, 1413, 1309, 1091; 1H NMR (CDCl3): δ 7.51
(d, J = 7.2 Hz, 2H, ArH), 7.41 (dd, J = 7.6 Hz, 2H, ArH), 7.35 (d,
J = 7.6 Hz, 1H, ArH), 5.70 (dd, J = 1.2, 6.4 Hz, 1H, –NCH), 5.40 (s,
1H, ArCH), 3.82 (m, 1H, –NCH2), 3.12 (m, 1H, –NCH2), 2.17 (m, 2H,
–CH2), 2.03 (m, 1H, –CH2), 1.77 (m, 1H, –CH2) [lit.22 1.69–2.26 (m,
4H, CH2), 3.07–3.17 (m, 1H, CHHN), 3.74–3.84 (m, 1H, CHHN),
5.45 (s, 1H,CHC=O), 5.59–5.63 (m, 1H, NCHO), 7.30–7.50 (m, 5H,
ArH)]; 13C NMR: δ 173.6, 136.2, 128.7, 128.4, 125.7, 94.3, 83.4, 42.4,
31.5, 24.1 (lit.22 24.3, 31.50, 43.0, 83.7, 92.7, 126.9, 128.5, 128.7,
135.6, 173.1); ESI-MS m/z: 226.09 [M+Na]+. 1H NMR (CDCl3):
δ 7.41 (d, J = 4.4 Hz, 3H, ArH), 7.37 (m, 2H, ArH), 5.63 (dd, J = 0.8,
5.2 Hz, 1H, –NCH), 5.48 (s, 1H, ArCH), 3.81 (m, 1H, –NCH2), 3.16
(m, 1H, –NCH2), 2.24 (m, 1H, –CH2), 2.08 (m, 2H, –CH2), 1.92 (m,
1H, –CH2); 13C NMR: δ 173.2, 135.9, 128.6, 128.5, 126.9, 92.6, 83.3,
43.1, 31.7, 24.4.
1-[2-(2-Methoxyphenyl)-2-oxoacetyl]piperidine-2-carboxylic acid
(1e): Pale-yellow solid, m.p. 156.7–157.7 °C; IR (cm−1): 3545, 3471,
1
3417, 3404, 3234, 1639, 1620, 752, 611, 476; H NMR (CD3Cl, 4:1
mixture of trans–cis amide rotamers, data for major rotamer): δ 8.56
(s, 1H, –COOH), 7.95 (d, J = 7.6 Hz, 1H, ArH), 7.59 (t, J = 7.6 Hz,
1H, ArH), 7.08 (t, J = 7.6 Hz, 1H, ArH), 7.00 (d, J = 8.4 Hz, 1H,
ArH), 5.37 (d, J = 4.4 Hz, 1H, –NCH), 3.90 (s, 3H, –OCH3), 3.55
(d, J = 13.2 Hz, 1H, –NCH2), 3.38 (t, J = 12.4 Hz, 1H, –NCH2), 2.36
(d, J = 13.2 Hz, 1H, –CH2), 1.82 (m, 1H, –CH2), 1.4–1.7 (m, 4H,
–CH2CH2); 13C NMR: δ 190.0, 174.8, 168.6, 160.5, 136.2, 131.1,
123.1, 121.1, 112.1, 56.02, 51.5, 44.0, 26.7, 24.6, 21.1; ESI-MS m/z:
314. 16 [M+Na]+; HR-MS (ESI) m/z: Calcd for C15H17NO5: 314.1004,
found 314.1002 [M+ Na]+.
2-(2-Oxo-2-phenylacetamido)-3-phenylpropanoic acid (1f): Pale-
yellow solid, 114–116 °C; IR (cm−1): 3535, 3471, 3420, 3237, 1639,
1617, 611, 733; 1H NMR (CD3Cl): δ 10.40 (s, 1H, –COOH), 8.20 (d,
J = 7.6 Hz, 2H, ArH), 7.62 (dd, J = 7.6, 13.6 Hz, 2H, ArH,NH), 7.46
(t, J = 7.6 Hz, 2H, ArH), 7.30 (m, 3H, ArH), 7.24 (d, J = 6.8 Hz, 2H,
ArH), 5.02 (dd, J = 7.2, 13.2 Hz, 1H, –NCH), 3.35 (dt, J = 1.2, 10.4
Hz, 1H, –ArCH2), 3.18 (dt, J = 1.2, 10.4 Hz, 1H, –ArCH2); 13C NMR:
δ 187.3, 175.1, 162.2, 135.5, 134.7, 132.9, 131.1, 129.4, 128.8, 128.6,
127.4, 53.3, 37.6; ESI- MS m/z: 320.12 [M+Na]+.
We gratefully acknowledge financial support from National
Natural Science Fund Committee (No. 20972113).
2-(N-Methyl-2-oxo-2-phenylacetamido)acetic acid (1g): White
solid, m.p. 111.9–112.5 °C; IR (cm−1): 3513, 3449, 3394, 1652, 1633,
1
669, 547, 444; H NMR (CD3Cl, 3.5:1 mixture of trans–cis amide
Received 12 November 2012; accepted 6 January 2013
Paper 1201622 doi: 10.3184/174751913X13594855388300
Published online: 12 March 2013
rotamers, data for major rotamer): δ 9.33 (s, 1H, –COOH), 8.05 (d, J
= 7.6 Hz, 2H, ArH), 7.67 (t, J = 7.6 Hz, 1H, ArH), 7.55 (t, J = 8 Hz,
2H, ArH), 4.34 (s, 2H, –NCH2), 3.05 (s, 3H, –NCH3); 13C NMR: δ
191.1, 172.7, 168.2, 135.1, 132.8, 129.9, 129.2, 48.1, 36.34; ESI-MS
m/z: 244.12 [M+Na]+; HR-MS (ESI) m/z: Calcd for C11H11NO4:
244.0586, found 244.0588 [M+Na]+.
References
1
2
3
T. Konomi and H. Tani, J. Polym. Sci., Part A, 1969, 7, 2255.
A. Ishida and T. Mukaiyama, Bull. Chem. Soc. Jpn, 1978, 51, 2077.
C.Y. Li, W. Tsai, A.G. Damu, E.J. Lee, T.S. Wu, N.X. Dung, T.D. Thang
and L. Thanh, J. Agric. Food Chem., 2007, 55, 9436.
H. Sasaki,Y. Mori, J. Nakamura and J. Shibasaki, J. Med. Chem., 1991, 34,
628.
1-(2-Phenylacetyl)pyrrolidin-2-one (2a): Yellow solid, m.p. 39–
40 °C (lit.4 40–41 °C), IR(cm−1): 3035, 2975, 2955, 1639, 1626, 614,
476; 1H NMR (CDCl3): δ 7.30 (m, 5H, ArH), 4.28 (s, 2H, ArCH2CO),
3.82 (t, J = 7.2 Hz, 2H, –NCH2), 2.61 (t, J = 8.0 Hz, 2H, NCOCH2),
2.03 (m, 2H, –NCH2CH2); 13C NMR: δ 175.3(C=O), 172.3 (C=O),
134.1, 129.7, 128.4, 126.9(CArH), 45.7(–ArCH2CO), 42.9(–NCH2),
33.7(CH2), 17.1(CH2); ESI-MS m/z: 226.11 [M+Na]+.
4
5
6
7
I. Akihiko, B. Takashi and M. Teruaki, Chem. Lett., 1976, 7, 711.
R. Fuks and H.G. Viehe, Tetrahehron, 1969, 25, 5721.
R. Pagadala, J.S. Meshram, H.N. Chopde, V. Jetti and V. Udayini,
J. Heterocyclic Chem., 2011, 48, 1067.
1-(2-Phenylacetyl)piperidin-2-one (2c): Yellow liquid, IR(cm−1):
3237, 2959, 2943, 1639, 1617, 608, 480; 1H NMR (CDCl3): δ 7.31 (m,
5H, ArH), 4.28 (s, 2H, ArCH2), 3.75 (t, J = 5.6 Hz, 2H, –NCH2), 2.56
(t, J = 6.8 Hz, 2H, –NCOCH2), 1.85 (m, 4H, –CH2CH2); 13C NMR:
δ 174.9, 173.4, 135.0, 129.6, 128.3, 126.7, 45.6, 44.3, 34.8, 22.4, 20.3;
ESI-MS m/z: 240.12 [M+Na]+.
8
9
J. Zhang and S.H. Hong, Org. Lett., 2012, 14, 4646.
R.T. Wang, C.F. Chen, E. Duesler and P.S. Mariano, J. Org. Chem., 2004,
69, 1215.
10 B. Akermark, N.G. Johansson and B. Sjoberg, Tetrahehron Lett., 1969,
5,371.
1-[2-(4-Methoxyphenyl)acetyl]piperidin-2-one (2d):Yellow liquid,
IR(cm−1): 3240, 2993, 1642, 1623, 736, 627, 486; 1H NMR (CDCl3):
δ 7.19 (d, J = 8.8 Hz, 2H, ArH), 6.87 (d, J = 8.8 Hz, 2H, ArH), 4.21 (s,
2H, ArCH2), 3.81 (s, 3H, –OCH3), 3.74 (t, J = 5.6 Hz, 2H, –NCH2),
11 A.G. Griesbeck and H.K. Heckroth, Synlett., 2002, 1, 131.
12 J.L. Jesuraj and J. Sivaguru, Chem. Commun., 2010, 46, 4791.
13 K.T. Li, Y.B. Lin and D.Y. Yang, Org. Lett., 2012, 14, 1190.
14 W.G. Bentrude and K.R. Darnall, Chem. Commun., 1969, 15, 862.
15 T. Goka, H. Shizoka and K. Matsui, J. Org. Chem.,1978, 43, 1361.
16 S. Maeda, K. Ohno and K. Morokuma, J. Phys. Chem. Lett., 2010, 1,
1841.
2.56 (t, J = 6.8 Hz, 2H, NCOCH2), 1.84 (m, 4H, –NCOCH2CH2); 13
C
NMR: δ 175.4, 173.4, 158.5, 130.7, 127.1, 113.8, 55.2, 44.7, 44.2,
34.9, 22.4, 20.3; ESI- MS m/z: 270.12 [M+Na]+.
1-[2-(2-Methoxyphenyl)acetyl]piperidin-2-one (2e): Yellow liquid,
IR(cm−1): 3237, 2978, 1639, 1617, 758, 614, 473; 1H NMR (CDCl3):
δ 7.27 (d, J = 7.6 Hz, 1H, ArH), 7.14 (d, J = 7.2 Hz, 1H, ArH), 6.93 (t,
J = 7.6 Hz, 1H, ArH), 6.89 (d, J = 8.0 Hz, 1H, ArH), 4.22 (s, 2H,
ArHCH2), 3.81 (s, 3H, –OCH3), 3.75 (t, J = 5.6 Hz, 2H, –NCH2), 2.58
(t, J = 6.8 Hz, 2H, –NCOCH2), 1.86 (m, 4H, –NCOCH2CH); 13C
NMR: δ 175.4, 173.7, 157.9, 131.2, 128.4, 124.7, 120.6, 110.7, 55.6,
44.3, 41.5, 34.9, 22.8, 20.5; ESI-MS m/z: 270.10 [M+Na]+; HR-MS
(ESI) m/z: Calcd for C14H17NO3: 270.1106, found 270.1104
[M+Na]+.
17 J.C. Dalton, P.A. Wriede and N.J. Turro, J. Am. Chem. Soc., 1970, 92,
1318.
18 J.C. Dalton and S.J. Tremont, J. Am. Chem. Soc., 1975, 97, 6916.
19 M.L. Yarchak, J.C. Dalton and W.H. Saunders, J. Am. Chem. Soc., 1973,
95, 5228.
20 X.C. Cai, M. Yamaji, M. Sakamoto, M. Fujitsuka and T. Majima, Chem.
Phys. Lett., 2007, 443, 248.
21 A.J.L. Cooper, J.Z. Ginos and A. Meister, Chem. Rev., 1983, 83, 321.
22 A.N. Cayley, K.A. Gallagher, M.C. Menard, J.P. Schmidt, L.J. Diorazio
and R.J.K. Taylor, Synthesis, 2008, 23, 384.

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