Oxidative Amidation of Aromatic Ethers
COMMUNICATION
6-Fluoro-4-tosyl-1-oxa-4-azaspiro
[4.5]deca-6,9-dien-8-one (2i): Following
66.1, 47.8 ppm; HRMS (ESI+): m/z calcd for C18H14N2O6SNa: 409.0465
[M+Na]+; found: 409.0464.
the general procedure by using N-[2-(2-fluorophenoxy)ethyl]-4-methyl-
benzenesulfonamide as the substrate gave compound 2i (90% yield,
40% conversion). 1H NMR (400 MHz, CDCl3): d=7.69 (d, J=8.4 Hz,
2H), 7.33 (d, J=8.4 Hz, 2H), 6.44 (t, J=10.0 Hz, 1H), 6.21 (dd, J=10.0,
0.8 Hz, 1H), 5.87 (dd, J=12.8, 2.0 Hz, 1H), 4.31–4.21 (m, 2H), 3.82–3.73
(m, 2H), 2.45 ppm (s, 3H); 13C NMR (100 MHz, DMSO): d=186.7,
186.5, 144.8, 144.2, 135.6, 130.4, 128.6, 127.8, 110.6, 85.6, 67.4, 47.6,
21.5 ppm; HRMS (ESI+): m/z calcd for C17H19NO5SNa: 346.0520
[M+Na]+; found: 346.0523.
4-(4-Methoxyphenylsulfonyl)-1-oxa-4-azaspiroACTHNUTRGNEUG[N 4.5]deca-6,9-dien-8-one
(2p): Following the general procedure by using 4-methoxy-N-(2-phenox-
yethyl)benzenesulfonamide as the substrate gave compound 2p (66%
yield, 54% conversion). 1H NMR (400 MHz, CDCl3): d=7.74 (d, J=
8.8 Hz, 2H), 6.98 (d, J=8.8 Hz, 2H), 6.51 (d, J=10.4 Hz, 2H), 6.20 (d,
J=10.4 Hz, 2H), 4.17 (t, J=6.0 Hz, 2H), 3.89 (s, 3H), 3.73 ppm (t, J=
6.0 Hz, 2H); 13C NMR (100 MHz, DMSO): d=185.3, 163.4, 145.1, 130.6,
130.2, 129.1, 115.0, 86.1, 65.8, 56.2, 47.2 ppm; HRMS (ESI+): m/z calcd
for C15H15NO5SNa: 344.0563 [M+Na]+; found: 344.0560.
6,7-Dichloro-4-tosyl-1-oxa-4-azaspiroACTHNUGTRNEUNG[4.5]deca-6,9-dien-8-one (2j): Fol-
lowing the general procedure by using N-[2-(2,3-dichlorophenoxy)ethyl]-
4-methylbenzenesulfonamide as the substrate gave compound 2j (80%
yield, 24% conversion). 1H NMR (400 MHz, CDCl3): d=7.66 (d, J=
8.4 Hz, 2H), 7.33 (d, J=8.4 Hz, 2H), 6.68 (d, J=10.0 Hz, 1H), 6.38 (d,
J=10.0 Hz, 1H), 4.44–4.39 (m, 1H), 4.27–4.22 (m, 1H), 3.89–3.84 (m,
1H), 3.82–3.75 (m, 1H), 2.46 ppm (s, 3H); 13C NMR (100 MHz, DMSO):
d=176.7, 149.1, 145.3, 144.8, 135.7, 132.8, 130.4, 127.8, 126.9, 88.8, 67.6,
47.4, 21.6 ppm; HRMS (ESI+): m/z calcd for C17H19NO5SNa: 395.9834
[M+Na]+; found: 395.9881.
6-Chloro-4-(4-methoxyphenylsulfonyl)-1-oxa-4-azaspiroACTHNUTRGENUGN[4.5]deca-6,9-
dien-8-one (2q): Following the general procedure by using N-[2-(2-chlor-
ophenoxy)ethyl]-4-methoxybenzenesulfonamide as the substrate gave
compound 2q (75% yield, 34% conversion). 1H NMR (400 MHz,
CDCl3): d=7.77 (d, J=8.8 Hz, 2H), 6.98 (d, J=8.8 Hz, 2H), 6.79 (d, J=
10.0 Hz, 1H), 6.42 (s, 1H), 6.25 (d, J=10.0 Hz, 1H), 4.42–4.37 (m, 1H),
4.25–4.20 (m, 1H), 3.89 (s, 3H), 3.78 ppm (t, J=6.4 Hz, 2H); 13C NMR
(100 MHz, DMSO): d=183.8, 163.5, 153.2, 144.9, 130.3, 130.1, 129.8,
127.9, 115.0, 87.3, 67.4, 56.3, 47.4 ppm; HRMS (ESI+): m/z calcd for
C15H14ClNO5SNa: 387.0173 [M+Na]+; found: 378.0175.
4-(4-Nitrophenylsulfonyl)-1-oxa-4-azaspiroACTHNUTRGNEU[GN 4.5]deca-6,9-dien-8-one (2k):
Following the general procedure by using 4-nitro-N-(2-phenoxyethyl)ben-
zenesulfonamide as the substrate gave compound 2k (38% yield, 90%
conversion). 1H NMR (400 MHz, CDCl3): d=8.39 (d, J=8.8 Hz, 2H),
8.01 (d, J=8.8 Hz, 2H), 6.48 (d, J=10.0 Hz, 2H), 6.26 (d, J=10.0 Hz,
2H), 4.22 (t, J=6.0 Hz, 2H), 3.77 ppm (t, J=6.0 Hz, 2H); 13C NMR
(100 MHz, DMSO): d=185.2, 150.5, 144.5, 144.4, 129.5, 125.2, 86.6, 66.0,
47.5 ppm; HRMS (ESI+): m/z calcd for C14H12N2O6SNa: 359.0308
[M+Na]+; found: 359.0303.
4-(4-Methoxyphenylsulfonyl)-6-methyl-1-oxa-4-azaspiroACTHNUTRGENUGN[4.5]deca-6,9-
dien-8-one (2r): Following the general procedure by using 4-methoxy-N-
[2-(ortho-tolyloxy)ethyl]benzenesulfonamide as the substrate gave com-
pound 2r (72% yield, 90% conversion). 1H NMR (400 MHz, CDCl3):
d=7.72 (d, J=8.4 Hz, 2H), 6.97 (d, J=8.4 Hz, 2H), 6.37 (d, J=10.0 Hz,
1H), 6.13 (d, J=10.0 Hz, 2H), 4.28–4.23 (m, 1H), 4.20–4.14 (m, 1H),
3.89 (s, 3H), 3.83–3.77 (m, 1H), 3.74–3.69 (m, 1H), 1.92 ppm (s, 3H);
13C NMR (100 MHz, DMSO): d=185.3, 163.4, 156.1, 144.6, 130.6, 130.1,
128.6, 128.2, 115.0, 87.8, 66.4, 56.2, 47.4, 17.7 ppm; HRMS (ESI+): m/z
calcd for C16H17NO5SNa: 358.0719 [M+Na]+; found: 358.0717.
6-Methyl-4-(4-nitrophenylsulfonyl)-1-oxa-4-azaspiroACHTNUTRGNEUNG[4.5]deca-6,9-dien-8-
one (2l): Following the general procedure by using 4-nitro-N-[2-(ortho-
tolyloxy)ethyl]benzenesulfonamide as the substrate gave compound 2l
(63% yield, 90% conversion). 1H NMR (400 MHz, CDCl3): d=8.39 (d,
J=8.8 Hz, 2H), 7.99 (d, J=8.8 Hz, 2H), 6.35 (d, J=9.6 Hz, 1H), 6.19 (d,
J=9.6 Hz, 2H), 4.34–4.29 (m, 1H), 4.22–4.16 (m, 1H), 3.86–3.74 (m,
2H), 1.88 ppm (s, 3H); 13C NMR (100 MHz, DMSO): d=184.8, 154.1,
150.4, 144.4, 141.9, 129.3, 129.2, 128.8, 124.4, 88.6, 66.1, 47.5, 17.8 ppm;
HRMS (ESI+): m/z calcd for C15H14N2O6SNa: 373.0465 [M+Na]+;
found: 373.0466.
4-(4-Methoxyphenylsulfonyl)-6,7-dimethyl-1-oxa-4-azaspiroACTHNUTRGNEUGN[4.5]deca-6,9-
dien-8-one (2s): Following the general procedure by using N-[2-(2,3-di-
methylphenoxy)ethyl]-4-methoxybenzenesulfonamide as the substrate
gave compound 2s (57% yield, 70% conversion). 1H NMR (400 MHz,
CDCl3): d=7.68 (d, J=8.4 Hz, 2H), 6.96 (d, J=8.4 Hz, 2H), 6.41 (d, J=
10.0 Hz, 1H), 6.15 (d, J=10.0 Hz, 1H), 4.29–4.24 (m, 1H), 4.18–4.12 (m,
1H), 3.88 (s, 3H), 3.84–3.75 (m, 2H), 1.85 (s, 3H), 1.75 ppm (s, 3H);
13C NMR (100 MHz, DMSO): d=184.8, 163.3, 148.7, 144.0, 133.6, 130.8,
130.0, 127.7, 114.9, 88.3, 85.9, 56.7, 47.5, 14.8, 11.4 ppm; HRMS (ESI+):
m/z calcd for C17H19NO5SNa: 372.0876 [M+Na]+; found: 372.0873.
6-Chloro-4-(4-nitrophenylsulfonyl)-1-oxa-4-azaspiroACHTNUTRGNEUNG[4.5]deca-6,9-dien-8-
one (2m): Following the general procedure by using N-[2-(2-chlorophe-
noxy)ethyl]-4-nitrobenzenesulfonamide as the substrate gave compound
2m (94% yield, 55% conversion). H NMR (400 MHz, CDCl3): d=8.41–
3’-(4-Methoxyphenylsulfonyl)-4H-spiro(naphthalene-1,2’-oxazolidin)-4-
one (2t): Following the general procedure by using 4-methoxy-N-[2-
(naphthalen-1-yloxy)ethyl]benzenesulfonamide as the substrate gave
compound 2t (51% yield, 65% conversion). 1H NMR (400 MHz,
CDCl3): d=8.08 (s, J=7.6 Hz, 1H), 7.46 (t, J=7.6 Hz, 1H), 7.38–7.31 (m,
1H), 7.27 (d, J=7.6 Hz, 2H), 7.21 (d, J=7.6 Hz, 2H), 6.81–6.77 (m, 3H),
6.61 (d, J=10.4 Hz, 1H), 4.43–4.38 (m, 1H), 4.33–4.27 (m, 1H), 3.98–3.93
(m, 1H), 3.84 (s, 3H), 3.81–3.75 ppm (m, 1H); 13C NMR (100 MHz,
DMSO): d=184.0, 163.0, 145.3, 140.6, 133.4, 131.3, 130.6, 129.8, 129.5,
128.5, 128.1, 125.7, 114.7, 87.7, 66.0, 56.2, 47.3 ppm; HRMS (ESI+): m/z
calcd for C19H17NO5SNa: 394.0720 [M+Na]+; found: 394.0748.
1
8.37 (m, 2H), 8.14–8.00 (m, 2H), 6.62 (d, J=9.6 Hz, 1H), 6.47 (d, J=
2.0 Hz, 1H), 6.30 (dd, J=9.6, 2.0 Hz, 1H), 4.46–4.41 (m, 1H), 4.29–4.24
(m, 1H), 3.92–3.87 (m, 1H), 3.81–3.76 ppm (m,1H); 13C NMR (100 MHz,
DMSO): d=183.7, 152.3, 150.6, 144.3, 143.8, 130.1, 129.4, 128.3, 125.3,
87.7, 67.5, 47.9 ppm; HRMS (ESI+): m/z calcd for C14H11ClN2O6SNa:
392.9919 [M+Na]+; found: 392.9922.
6,7-Dimethyl-4-(4-nitrophenylsulfonyl)-1-oxa-4-azaspiroACTHNUTRGENUGN[4.5]deca-6,9-
dien-8-one (2n): Following the general procedure by using N-[2-(2,3-di-
methylphenoxy)ethyl]-4-nitrobenzenesulfonamide as the substrate gave
compound 2n (35% yield, 90% conversion). 1H NMR (400 MHz,
CDCl3): d=8.38–8.35 (m, 2H), 7.95–7.92 (m, 2H), 6.38 (d, J=10.0 Hz,
1H), 6.20 (d, J=10.0 Hz, 1H), 4.35–4.30 (m, 1H), 4.20–4.10 (m, 1H),
3.84–3.81 (m, 2H), 1.89 (s, 3H), 1.75 ppm (s, 3H); 13C NMR (100 MHz,
DMSO): d=184.7, 150.4, 148.0, 144.3, 143.3, 134.0, 129.3, 128.2, 128.1,
125.1, 125.0, 88.8, 66.1, 47.8, 14.8, 11.4 ppm; HRMS (ESI+): m/z calcd
for C16H16N2O6SNa: 387.0621 [M+Na]+; found: 387.0619.
Acknowledgements
This work was financially supported by the National Science Foundation
of China (No. 21072131).
3’-(4-Nitrophenylsulfonyl)-4H-spiro(naphthalene-1,2’-oxazolidin)-4-one
(2o): Following the general procedure by using N-[2-(naphthalen-1-ylox-
y)ethyl]-4-nitrobenzenesulfonamide as the substrate gave compound 2o
Keywords: amidation · ethers · rhodium · rhodium acetate ·
sulfamides · transition-metal catalysis
1
(40% yield, 90% conversion). H NMR (400 MHz, CDCl3): d=8.14–8.10
(m, 3H), 7.50–7.47 (m, 1H), 7.40 (d, J=8.8 Hz, 2H), 7.22–7.18 (m, 1H),
7.01 (d, J=8.0 Hz, 1H), 6.87 (d, J=10.0 Hz, 1H), 6.50 (d, J=10.0 Hz,
1H), 4.49–4.45 (m, 1H), 4.41–4.35 (m, 1H), 4.13–4.08 (m, 1H), 3.80–
3.73 ppm (m, 1H); 13C NMR (100 MHz, DMSO): d=183.9, 150.1, 144.9,
144.2, 139.7, 133.4, 131.3, 130.2, 128.8, 128.6, 128.1, 125.8, 124.8, 88.0,
[1] a) J.-L. Liang, S.-X. Yuan, J.-S. Huang, W.-Y. Yu, C.-M. Che, Angew.
Chem. Eur. J. 2012, 18, 1077 – 1082
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1081