Pd(II)-Catalyzed Synthesis of Lactones and Lactams
J. Am. Chem. Soc., Vol. 118, No. 18, 1996 4269
Lactones. The following lactones are known compounds and have
spectral data in accord with the literature data: 2a, 2b, 3b, 2c, 3c, 2d,
3e, 2f, 3f, 2g, 3g, and 2h,37 3a,38 and 4a.39
Characterization Data for New Lactones. 9-Methyl-4,5-dihydro-
1-benzoxepin-2(3H)-one (4b): 1H NMR (CDCl3) δ 2.04-2.22 (m, 2H),
2.25 (s, 3H), 2.44 (t, 2H, J ) 7.41 Hz), 2.76 (t, 2H, J ) 7.30 Hz),
7.00-7.08 (m, 3H); 13C NMR (CDCl3) δ 16.20, 26.45, 28.30, 31.05,
125.40, 127.04, 128.30, 128.60, 128.81, 15.50, 171.74; MS m/e 176
[M+]. Anal. Calcd for C11H12O2: C, 74.98; H, 6.86. Found: C, 74.53;
H, 7.08.
7-Chloro-4,5-dihydro-1-benzoxepin-2(3H)-one (4c): 1H NMR
(CDCl3) δ 2.11-2.22 (m, 2H), 2.45 (t, 2H, J ) 7.34 Hz), 2.75 (t, 2H,
J ) 7.33 Hz), 7.00-7.22 (m, 3H); 13C NMR (CDCl3) δ 26.10, 28.08,
30.90, 120.60, 128.08, 129.40, 130.70, 131.80, 150.21, 170.81; MS
m/e 196 [M+]. Anal. Calcd for C10H9ClO2: C, 61.80; H, 4.61.
Found: C, 61.75; H, 4.64.
m/e 163 [M+]. Anal. Calcd for C10H13NO (Z + E): C, 73.60; H,
8.03; N, 8.60. Found: C, 73.33; H, 8.18; N, 8.66.
Synthesis of 2-Allyl-6-methoxyaniline (8d). 8d was prepared by
the Claisen rearrangement of 2-methoxy-N-allylaniline which can be
prepared according to a literature method:29,40 yield 40%; oil [eluant
n-hexane/ether (9/1)]; 1H NMR (CDCl3) δ 3.28-3.32 (m, 2H), 3.79-
3.82 (m, 5H), 5.04-5.08 (m, 1H), 5.12 (d, 1H, J ) 0.73 Hz), 5.86-
6.00 (m, 1H), 6.70 (s, 3H); 13C NMR (CDCl3) δ 36.19, 55.54, 108.44,
135.71, 115.85, 117.64, 122.09, 124.06, 134.37, 147.23; MS m/e 163
[M+]. Anal. Calcd for C10H13NO: C, 73.60; H, 8.03; N, 8.60.
Found: C, 73.32; H, 8.00; N, 8.73.
General Procedure for the Carbonylation of 2-Aminostyrenes 5
and 2-Allylanilines 8. A mixture of 1.0 mmol of 5 or 8, 0.010 mmol
of palladium(II) catalyst, and 0.04 mmol of dppb or 0.08 mmol of
PPh3 or PCy3 (see Tables 1 and 2 for the reaction conditions) was
dissolved in 5 mL of dry solvent and placed in a 45 mL autoclave.
The autoclave was purged, pressurized, and then heated (see Tables 1
and 2 for the time, temperature, and pressure in each case). The reaction
was then cooled to room temperature, filtered through Celite or silica
gel, and concentrated by rotary evaporation. The separation and the
purification of lactams were achieved by silica gel chromatography
and by HPLC. The products were identified by comparison of spectral
data with those for authentic materials, where known, and by elemental
analysis as well as by spectral data [IR, NMR (1H, 13C), MS].
Lactams. The following lactams are known compounds and have
spectral data in accord with the literature data: 6a,41 7a,41 6b,42 7b,32
6c,43 7c,44 7e,45 6f,41,43 7f,31 9a or 6c,43 10a or 7c,44 11a,46 11c,47 10f,48
11f,48 9g,49 10g,50 11g,51 and 14.52
5-Methyl-4-hydro-1-benzoxepin-2(3H)-one (4d): 1H NMR (CDCl3)
δ 1.34 (d, 3H, J ) 6.82 Hz), 1.52-1.56 (m, 1H), 2.20-2.40 (m, 3H),
3.20-3.35 (m, 1H), 7.10-7.40 (m, 4H); 13C NMR (CDCl3) δ 18.00,
31.84, 31.90, 35.50, 119.80, 126.30, 126.60, 128.50, 129.0, 152.10,
172.40; MS m/e 176 [M+]. Anal. Calcd for C11H12O2: C, 74.98; H,
6.86. Found: C, 75.09; H, 6.88.
1
5-Methyl-7-tert-butyl-4-hydro-1-benzoxepin-2(3H)-one (4e): H
NMR (CDCl3) δ 1.22 (s, 9H), 1.28 (d, 3H, J ) 7.10 Hz), 1.44-1.64
(m, 1H), 2.34-2.38 (m, 3H), 3.00-3.18 (m, 1H), 6.56-7.40 (m, 3H);
13C NMR (CDCl3) δ 17.18, 30.96, 31.20, 31.30, 34.40, 34.70, 118.30,
122.20, 124.30, 132.60, 148.60, 148.90, 171.90; MS m/e 232 [M+].
Anal. Calcd for C15H20O2: C, 77.55; H, 8.68. Found: C, 77.65; H,
8.58.
4-Methyl-4,5-dihydro-1-benzoxepin-2(3H)-one (4f): 1H NMR
(CDCl3) δ 0.93 (d, 3H, J ) 6.60 Hz), 2.04-2.10 (m, 1H), 2.43 (q, 1H,
J ) 6.40 Hz), 2.49-2.56 (m, 3H), 2.93 (qd, 1H, J ) 7.44 Hz, 6.40
Hz), 7.04-7.26 (m, 4H); 13C NMR (CDCl3) δ 20.30, 33.63, 36.08,
38.48, 119.16, 125.54, 128.28, 128.94, 130.20, 151.72, 170.54; MS
m/e 176 [M+]. Anal. Calcd: C, 74.98; H, 6.90. Found: C, 74.60; H,
6.93.
Characterization Data for New Lactams. 3-Ethyl-7-methoxy-
1
oxindole 6d or 9d: H NMR (CDCl3) δ 0.91 (t, 3H, J ) 7.33 Hz),
2.03 (qd, 2H, J ) 7.33 Hz, 5.48 Hz), 3.47 (t, 1H, J ) 5.30 Hz), 3.87
(s, 3H), 6.79-6.87 (m, 2H), 6.95-7.03 (m, 1H), 8.77 (br s, 1H); 13C
NMR (CDCl3) δ 10.64, 24.18, 48.39, 56.28, 110.84, 117.05, 123.24,
130.99, 131.30, 144.42, 180.51; MS m/e 191 [M+]. Anal. Calcd for
C11H13NO3: C, 69.08; H, 6.87; N, 7.32. Found: C, 69.16; H, 6.89; N,
7.15.
4,5-Dihydro-1-benzo[g]benzoxepin-2-(3H)-one (4g): 1H NMR
(CDCl3) δ 2.20-2.40 (m, 2H), 2.50 (t, 2H, J ) 6.60 Hz), 3.25 (t, 2H,
J ) 6.96 Hz), 7.26 (d, 1H, J ) 8.08 Hz), 7.43-7.60 (m, 2H), 7.74-
7.90 (m, 2H), 7.99-8.04 (d, 1H, J ) 8.40 Hz); 13C NMR (CDCl3) δ
22.50, 26.60, 31.50, 119.00, 122.90, 124.30, 125.40, 127.00, 128.50,
128.80, 131.60, 131.90, 149.30, 171.10; MS m/e 212 [M+]. Anal. Calcd
for C14H12O2: C, 79.50; H, 5.70. Found: C, 79.17; H, 5.54.
4,5-Dihydro-1-benzo[i]benzoxepin-2(3H)-one (4h): 1H NMR (CDCl3)
δ 2.16-2.28 (m, 2H), 2.40 (t, 2H, J ) 7.50 Hz), 2.88 (t, 2H, J ) 7.20
Hz), 7.20 (d, 1H, J ) 8.20 Hz), 7.38-7.45 (m, 2H), 7.58 (d, 1H, J )
8.24 Hz), 7.72-8.08 (m, 2H); 13C NMR (CDCl3) δ 27.50, 28.44, 31.41,
121.41, 125.42, 125.50, 126.30, 126.65, 127.10, 127.60, 133.10, 133.70,
146.60, 171.84; MS m/e 212 [M+]. Anal. Calcd: C, 79.50; H, 5.70.
Found: C, 79.52; H, 5.58.
Pentacyclic Lactone 4i: 1H NMR (CDCl3) δ 0.91 (d, 3H, J ) 7.20
Hz), 1.32 (d, 3H, J ) 6.81 Hz), 1.40-1.64 (m, 7H), 1.94-2.16 (m,
4H), 2.24-2.52 (m, 6H), 2.85-2.88 (m, 2H), 3.09-3.15 (m, 1H), 6.80
(s, 1H), 7.12 (s, 1H); 13C NMR (CDCl3) δ 13.82, 17.50, 21.55, 25.81,
26.33, 28.97, 31.28, 31.31, 31.54, 35.02, 35.80, 38.10, 44.30, 47.90,
50.37, 119.20, 122.60, 130.70, 136.30, 137.20, 149.40, 172.20, 220.70;
MS m/e 352 [M+]. Anal. Calcd: C, 78.40; H, 7.95. Found: C, 78.06;
H, 7.85.
3,4-Dihydro-8-methoxy-3-methyl-2(1H)-quinolinone 7d or 10d:
1H NMR (CDCl3) δ 1.29 (d, 3H, J ) 6.5 Hz), 2.64-2.75 (m, 2H),
2.94-3.02 (m, 1H), 3.86 (s, 3H), 6.75-6.79 (m, 2H), 6.90-6.98 (m,
1H), 7.75 (br s, 1H); 13C NMR (CDCl3) δ 15.25, 33.30, 34.74, 55.62,
108.83, 119.92, 112.54, 123.82, 130.23, 145.54, 173.10; MS m/e 191
[M+]. Anal. Calcd for C11H13NO3: C, 69.08; H, 6.87; N, 7.32.
Found: C, 69.16; H, 6.89; N, 7.15.
5,6-Dioxolo-3-ethyloxindole (6e): 1H NMR (CDCl3) δ 0.90 (t, 3H,
J ) 7.47 Hz), 1.97 (td, 2H, J ) 7.47 Hz, 5.67 Hz), 3.39 (t, 1H, J )
5.67 Hz), 5.93 (s, 2H), 6.51 (s, 1H), 6.75 (s, 1H), 8.60 (br s, 1H); 13
C
NMR (CDCl3) δ 9.77, 23.26, 47.37, 93.35, 100.96, 105.52, 121.11,
135.59, 143.07, 146.94, 180.84; MS m/e 208 [M+]. Anal. Calcd for
C11H11NO3: C, 64.37; H, 5.41; N, 6.82. Found: C, 64.41; H, 5.36; N,
7.11.
1
3-(Furylmethyl)oxindole (6g): H NMR (CDCl3) δ 2.98 (dd, 1H,
J ) 9.50 Hz, 15.0 Hz), 3.48 (dd, 1H, J ) 4.65 Hz, 15.0 Hz), 3.82 (dd,
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Synthesis of 2-(1-Propenyl)-6-methoxyaniline (5d). 5d was
prepared using ethyltriphenylphosphonium bromide and 3-methoxy-
2-nitrobenzaldehyde:28 yield 70%; oil [eluant n-hexane/ether (9/1); Z/E
1
) 70/30; H NMR (CDCl3) δ 1.72-1.77 (dd, 3H, J ) 1.75, 6.88 Hz)
(Z), 1.87-1.91 (dd, 3H, J ) 1.69, 6.90 Hz) (E), 3.83-3.86 (m, 5H) (Z
+ E), 5.82-6.15 (m, 1H) (Z + E), 6.28-6.40 (m, 1H), 6.67-6.71 (m,
3H) (Z + E); 13C NMR (CDCl3) (Z + E) δ 14.55, 18.82, 55.43, 55.52,
108.44, 115.85, 117.64, 122.09, 124.06, 134.37, 135.71, 147.23; MS
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