The Journal of Organic Chemistry
Note
4
7
.21 (q, J = 7.1 Hz, 1.48H)], [1.33 (t, J = 7.1 Hz, 0.78H), 1.25 (t, J =
[7.46−7.40 (m, 0.66H), 7.38−7.32 (m, 0.34H)], [4.26 (q, J = 7.1 Hz,
0.68H), 4.20 (q, J = 7.1 Hz, 1.32H)], [1.32 (t, J = 7.1 Hz, 1.02H),
1.24 (t, J = 7.1 Hz, 1.98H)]; C{ H} NMR (126 MHz, including
.1 Hz, 1.22H)]; 1 C{ H} NMR (126 MHz, CDCl , including 26%
3
1
3
enol
enol
enol
13
1
enol tautomer) δ 191.1, 172.9 , 169.5 , 167.0, 142.4, 139.9
,
enol
enol
enol
enol
enol
enol
1
9
37.7 , 137.4, 135.4 , 135.0, 130.4, 130.2 , 127.6, 125.2 , 94.5,
34% enol tautomer) δ 191.4, 172.7 , 168.7 , 166.8, 154.0,
enol
enol
enol
enol
enol
enol
enol
enol
4.2 , 88.2 , 61.6, 60.5 , 45.8, 14.3 , 14.1.
Ethyl 3-(4-Iodophenyl)-3-oxopropanoate (3ma). According to
the general procedure, 4-iodo-N-phenyl-N-tosylbenzamide (143.2 mg,
.3 mmol) afforded ethyl 3-(4-iodophenyl)-3-oxopropanoate (3ma)
77.3 mg, 0.24 mmol, 81%) as a colorless liquid by silica gel column
151.8 , 149.9, 147.4 , 135.8, 133.4 , 131.4, 129.3 , 123.7,
2
9
enol
enol
enol
enol
123.3 , 88.6 , 61.7, 60.6 , 46.0, 14.2 , 14.0.
3
0
Ethyl 3-(Furan-3-yl)-3-oxopropanoate (3ra). According to the
general procedure, N-phenyl-N-tosylfuran-3-carboxamide (102.4 mg,
0.3 mmol) afforded ethyl 3-(furan-3-yl)-3-oxopropanoate (3ra) (49.7
mg, 0.27 mmol, 91%) as a brown liquid by silica gel column
0
(
1
chromatography (eluent: n-hexane/EtOAc = 9:1): H NMR (500
MHz, CDCl , including 24% enol tautomer) δ [12.54 (s, 0.24H), 5.64
1
3
chromatography (eluent: n-hexane/EtOAc = 9:1): H NMR (500
(
8
0
s, 0.24H), 3.94 (s, 1.52H)], [7.84 (d, J = 8.6 Hz, 1.52H), 7.75 (d, J =
.6 Hz, 0.48H)], [7.64 (d, J = 8.6 Hz, 1.52H), 7.48 (d, J = 8.6 Hz,
.48H)], [4.26 (q, J = 7.1 Hz, 0.48H), 4.20 (q, J = 7.1 Hz, 1.52H)],
MHz, CDCl , including 12% enol tautomer) δ [12.20 (s, 0.12H), 5.35
3
(
0
6
s, 0.12H), 3.75 (s, 1.76H)], [8.10−8.06 (m, 0.88H), 7.90−7.87 (m,
.12H)], [7.47−7.44 (m, 0.88H), 7.43−7.41 (m, 0.12H)], [6.80−
.76 (m, 0.88H), 6.56−6.55 (m, 0.8 Hz, 0.12H)], 4.26−4.16 (m, 2H),
1
3
1
[
1.33 (t, J = 7.1 Hz, 0.72H), 1.25 (t, J = 7.1 Hz, 2.28H)]; C{ H}
enol
NMR (126 MHz, including 24% enol tautomer) δ 191.8, 173.0
1
1
,
13
1
[1.31 (t, J = 7.1 Hz, 0.36H), 1.25 (t, J = 7.1 Hz, 2.64H)]; C{ H}
70.3 , 167.1, 138.1, 137.7 , 135.2, 132.9 , 129.8, 127.5enol,
02.0, 97.9 , 87.7 , 61.6, 60.5 , 45.8, 14.3 , 14.1.
enol
enol
enol
enol
NMR (126 MHz, including 12% enol tautomer) δ 186.4, 172.8
1
1
,
enol
enol
enol
enol
66.9 , 166.2, 148.1, 144.5, 143.9 , 143.5 , 127.2, 121.8enol,
enol
enol
enol
2
9
Ethyl 3-(4-Cyanophenyl)-3-oxopropanoate (3na). According to
enol
enol
enol
enol
08.7, 107.4 , 87.4 , 61.6, 60.2 , 47.6, 14.3 , 14.0.
the general procedure, 4-cyano-N-phenyl-N-tosylbenzamide (112.9
mg, 0.3 mmol) afforded ethyl 3-(4-cyanophenyl)-3-oxopropanoate
33
Butyl 3-Oxo-3-phenylpropanoate (3ab). According to the
general procedure, N-phenyl-N-tosylbenzamide (105.4 mg, 0.3
mmol) afforded butyl 3-oxo-3-phenylpropanoate (3ab) (54.9 mg,
(3na) (41.1 mg, 0.19 mmol, 63%) as a white solid by silica gel column
1
chromatography (eluent: n-hexane/EtOAc = 9:1): mp 65−66 °C; H
NMR (500 MHz, CDCl , including 46% enol tautomer) δ [12.55 (s,
0
.25 mmol, 83% yield) as a colorless liquid by silica gel column
1
3
chromatography (eluent: n-hexane/EtOAc = 9:1): H NMR (500
0
1
7
7
1
.46H), 5.72 (s, 0.46H), 4.00 (s, 1.08H)], [8.04 (d, J = 8.6 Hz,
.08H), 7.86 (d, J = 8.7 Hz, 0.92H)], [7.79 (d, J = 8.6 Hz, 1.08H),
.71 (d, J = 8.6 Hz, 0.92H)], [4.28 (q, J = 7.1 Hz, 0.92H), 4.21 (q, J =
.1 Hz, 1.08H)], [1.34 (t, J = 7.1 Hz, 1.38H), 1.25 (t, J = 7.1 Hz,
MHz, CDCl , including 19% enol tautomer) δ [12.59 (s, 0.19H), 5.67
3
(s, 0.19H), 3.99 (s, 1.62H)], [7.94 (d, J = 7.4 Hz, 1.62H), 7.78 (d, J =
7
.2 Hz, 0.38H)], 7.63−7.39 (m, 3H), [4.21 (t, J = 6.7 Hz, 0.38H),
4
.15 (t, J = 6.7 Hz, 1.62H)], 1.72−1.55 (m, 2H), 1.47−1.27 (m, 2H),
13
.62H)]; C NMR (126 MHz, including 46% enol tautomer) δ
13
1
[0.96 (t, J = 7.4 Hz, 0.57H), 0.88 (t, J = 7.4 Hz, 2.43H)]; C{ H}
1
3
1
C{ H} NMR (126 MHz, CDCl , including 46% enol tautomer) δ
enol
3
NMR (126 MHz, including 19% enol tautomer) δ 192.5, 173.3
,
,
enol
enol
enol
enol
1
1
6
91.3, 172.7 , 168.6 , 166.7, 138.9, 137.6 , 132.6, 132.3
,
enol
enol
enol
enol
1
1
1
71.4 , 167.6, 136.0, 133.7, 133.4 , 131.2 , 128.7, 128.50
enol
enol
enol
enol
28.9, 126.5 , 118.2 , 117.7, 117.0, 114.4 , 89.7 , 61.8,
28.48, 126.0 , 87.4 , 65.3, 64.2 , 46.0, 30.7 , 30.5, 19.1enol,
9.0, 13.7 , 13.6.
Isopropyl 3-Oxo-3-phenylpropanoate (3ac). According to the
enol
enol
enol
enol
enol
enol
0.8 , 46.0, 14.2 , 14.0.
Ethyl 3-(4-Nitrophenyl)-3-oxopropanoate (3oa). According to
enol
3
1
34
the general procedure, 4-nitro-N-phenyl-N-tosylbenzamide (118.9
mg, 0.3 mmol) afforded ethyl 3-(4-nitrophenyl)-3-oxopropanoate
general procedure, N-phenyl-N-tosylbenzamide (105.4 mg, 0.3 mmol)
afforded isopropyl 3-oxo-3-phenylpropanoate (3ac) (55.7 mg, 0.27
mmol, 90% yield) as a colorless liquid by silica gel column
(3oa) (34.9 mg, 0.15 mmol, 49%) as a yellow solid by silica gel
column chromatography (eluent: n-hexane/EtOAc = 9:1): mp 69−70
1
chromatography (eluent: n-hexane/EtOAc = 9:1): H NMR (500
1
°
C; H NMR (500 MHz, CDCl , including 53% enol tautomer) δ
12.56 (s, 0.53H), 5.76 (s, 0.53H), 4.04 (s, 0.94H)], [8.33 (d, J = 8.9
3
MHz, CDCl , including 17% enol tautomer) δ [12.66 (s, 0.17H), 5.63
3
[
(s, 0.17H), 3.95 (s, 1.66H)], [7.94 (d, J = 7.2 Hz, 1.66H), 7.77 (d, J =
Hz, 0.94H), 8.27 (d, J = 8.9 Hz, 1.06H)], [8.11 (d, J = 8.9 Hz,
7
=
.0 Hz, 0.34H)], 7.62−7.37 (m, 3H), 5.18−5.03 (m, 1H), [1.31 (d, J
0
4
7
.94H), 7.93 (d, J = 9.0 Hz, 1.06H)], [4.30 (q, J = 7.1 Hz, 1.06H),
13 1
6.3 Hz, 1.02H), 1.22 (d, J = 6.3 Hz, 4.98H); C{ H} NMR (126
.22 (q, J = 7.1 Hz, 0.94H)], [1.35 (t, J = 7.1 Hz, 1.59H), 1.26 (t, J =
enol
enol
.1 Hz, 1.41H)]; 1 C{ H} NMR (126 MHz, including 53% enol
3
1
MHz, including 17% enol tautomer) δ 192.6, 172.8 , 171.3
167.0, 136.1, 133.6, 133.5 , 131.1 , 128.7, 128.5 , 128.4,
,
enol
enol
enol
enol
enol
enol
tautomer) δ 191.1, 172.6 , 168.3 , 166.7, 150.6, 149.2 , 140.3,
enol
enol
enol
enol
enol
enol
enol
enol
enol
126.0 , 87.8 , 69.0, 67.8 , 46.3, 21.9 , 21.6.
34
1
1
39.3 , 129.6, 126.9 , 124.0, 123.7 , 90.2 , 61.8, 60.9 , 46.2,
enol
tert-Butyl 3-Oxo-3-phenylpropanoate (3ad). According to the
general procedure, N-phenyl-N-tosylbenzamide (105.4 mg, 0.3 mmol)
afforded tert-butyl 3-oxo-3-phenylpropanoate (3ad) (60.8 mg, 0.28
mmol, 92% yield) as a colorless liquid by silica gel column
4.2 , 14.0.
3
2
Ethyl 3-(Naphthalen-2-yl)-3-oxopropanoate (3pa). According
to the general procedure, N-phenyl-N-tosyl-2-naphthamide (120.5
mg, 0.3 mmol) afforded ethyl 3-(naphthalen-2-yl)-3-oxopropanoate
1
chromatography (eluent: n-hexane/EtOAc = 9:1): H NMR (500
(3pa) (62.5 mg, 0.26 mmol, 86%) as a colorless liquid by silica gel
1
MHz, CDCl , including 13% enol tautomer) δ [12.73 (s, 0.13H), 5.58
3
column chromatography (eluent: n-hexane/EtOAc = 9:1): H NMR
500 MHz, CDCl , including 20% enol tautomer) δ [12.71 (s, 0.2H),
(s, 0.13H), 3.89 (s, 1.74H)], [7.94 (d, J = 7.4 Hz, 1.74H), 7.75 (d, J =
(
3
7
7
.1 Hz, 0.26H)], 7.61−7.37 (m, 3H), [1.54 (s, 1.17H), 1.43 (s,
5
8
7
1
.81 (s, 0.2H), 4.12 (s, 1.6H)], [8.45 (s, 0.8H), 8.36 (s, 0.2H)],
.05−7.75 (m, 4H), 7.64−7.49 (m, 2H), 5.81 (s, 1H), [4.30 (q, J =
.1 Hz, 0.4H), 4.24 (q, J = 7.1 Hz, 1.6H)], [1.36 (t, J = 7.1 Hz, 0.6H),
13 1
.83H)]; C{ H} NMR (126 MHz, CDCl , including 13% enol
3
enol
enol
enol
tautomer) δ 193.0, 173.1 , 170.8 , 166.7, 136.2, 133.7 , 133.5,
130.9 , 128.7, 128.4, 125.9 , 88.9, 82.0 , 81.1 , 47.4, 28.3
27.9.
Benzyl 3-Oxo-3-phenylpropanoate (3ae). According to the
general procedure, N-phenyl-N-tosylbenzamide (105.4 mg, 0.3 mmol)
afforded benzyl 3-oxo-3-phenylpropanoate (3ae) (51.9 mg, 0.20
mmol, 68% yield) as a colorless liquid by silica gel column
enol
enol
enol
enol
enol
1
3
1
,
.27 (t, J = 7.1 Hz, 2.4H)]; C{ H} NMR (126 MHz, CDCl ,
3
enol
enol
including 20% enol tautomer) δ 192.5, 173.2 , 171.2 , 167.6,
3
3
enol
enol
enol
1
1
1
35.8, 134.6 , 133.4, 132.8 , 132.4, 130.6, 129.7, 129.0 , 128.9,
28.7, 128.2 , 127.8, 127.7 , 127.6 , 127.0, 126.69enol, 126.66
enol
enol
enol
enol
,
enol
enol
enol
enol
23.8, 122.5 , 87.9 , 61.5, 60.4 , 46.1, 14.3 , 14.1.
2
8
Ethyl 3-Oxo-3-(pyridin-3-yl)propanoate (3qa). According to the
1
chromatography (eluent: n-hexane/EtOAc = 9:1): H NMR (500
general procedure, N-phenyl-N-tosylnicotinamide (105.7 mg, 0.3
mmol) afforded ethyl 3-(naphthalen-2-yl)-3-oxopropanoate (3qa)
MHz, CDCl , including 20% enol tautomer) δ [12.53 (s, 0.2H), 5.76
3
(s, 0.2H), 4.06 (s, 1.6H)], [7.94 (d, J = 7.2 Hz, 1.6H), 7.80 (d, J = 7.2
(
35.9 mg, 0.19 mmol, 62%) as a yellow liquid by silica gel column
1
Hz, 0.4H)], 7.63−7.30 (m, 8H), [5.27 (s, 0.4H), 5.21 (s, 1.6H)];
chromatography (eluent: n-hexane/EtOAc = 9:1): H NMR (500
1
3
1
MHz, CDCl , including 34% enol tautomer) δ [12.54 (s, 0.34H), 5.68
C{ H} NMR (126 MHz, CDCl , including 20% enol tautomer) δ
3
3
enol
enol
enol
(
1
1
s, 0.34H), 3.99 (s, 1.32H)], [9.13 (d, J = 1.5 Hz, 0.66H), 8.97 (d, J =
.4 Hz, 0.34H)], [8.79 (dd, J = 4.8, 1.5 Hz, 0.66H), 8.66 (dd, J = 4.8,
.4 Hz, 0.34H)], [8.25−8.19 (m, 0.66H), 8.06−8.01 (m, 0.34H)],
192.3, 172.9 , 171.8 , 167.3, 136.0, 135.8 , 135.4, 133.8,
133.3 , 131.4 , 128.8, 128.64 , 128.56, 128.50, 128.4, 128.3,
128.2 , 126.1 , 87.2 , 67.2, 66.1 , 45.9.
enol
enol
enol
enol
enol
enol
enol
5
949
J. Org. Chem. 2021, 86, 5943−5953