The Journal of Organic Chemistry
Note
1
(Z)-Methyl 2-(1-bromohexylidene)-5-oxoundecanoate (3ad): H
NMR (400 MHz, CDCl3) δ 3.74 (s, 3H), 2.78−2.69 (m, 4H), 2.60−
2.54 (m, 2H), 2.42−2.37 (m, 2H), 1.63−1.52 (m, 4H), 1.33−1.26 (m,
10H), 0.90−0.84 (m, 6H); 13C NMR (100 MHz, CDCl3) δ 209.9,
166.9, 142.0, 131.3, 52.0, 42.7, 40.5, 39.8, 31.6, 30.8, 29.2, 28.9, 28.4,
23.8, 22.5, 22.4, 14.0, 13.9 ppm; νmax(KBr)/cm−1 2929, 1718, 1260;
MS (EI) m/z 43, 85, 113, 235, 263, 295, 374. Anal. Calcd for
C18H31BrO3: C, 57.60; H, 8.32. Found: C, 57.23; H, 8.36.
29.9, 28.4, 22.4, 14.0 ppm; νmax(KBr)/cm−1 2930, 1721, 1678, 1602,
1267; MS (EI) m/z 77, 107, 135, 150, 317, 396; Anal. Calcd for
C19H25BrO4: C, 57.44; H, 6.34. Found: C, 57.29; H, 6.41.
(Z)-Ethyl 2-(1-bromoethylidene)-5-oxoheptanoate (3bc): 1H
NMR (400 MHz, CDCl3) δ 4.24−4.18 (m, 2H), 2.73 (t, J = 7.2
Hz, 2H), 2.60−2.51 (m, 5H), 2.45−2.40 (m, 2H), 1.29 (t, J = 7.2 Hz,
3H), 1.05 (t, J = 7.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 210.2,
166.3, 135.7, 131.8, 61.2, 40.1, 35.7, 29.2, 28.0, 14.2, 7.8 ppm;
νmax(KBr)/cm−1 2979, 1716, 1268; MS (EI) m/z 57, 151, 197, 276.
Anal. Calcd for C11H17BrO3: C, 47.67; H, 6.18. Found: C, 47.55; H,
6.21.
(Z)-Methyl 3-bromo-2-(3-cyclohexyl-3-oxopropyl)oct-2-enoate
1
(3ae): H NMR (400 MHz, CDCl3) δ 3.73 (s, 3H), 2.75 (t, J = 7.2,
2H), 2.70−2.67 (m, 2H), 2.63−2.59 (m, 2H), 2.41−2.28 (m, 1H),
1.83−1.75 (m, 4H), 1.66−1.55 (m, 4H), 1.33−1.20 (m, 8H), 0.88 (t, J
= 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 212.7, 167.0, 141.8,
131.5, 52.0, 50.7, 39.8, 38.4, 30.8, 29.2, 28.5, 28.4, 25.8, 25.6, 22.4, 13.9
ppm; νmax(KBr)/cm−1 2931, 2858, 1717, 1444, 1261; MS (EI) m/z 55,
83, 107, 121, 149, 195, 293, 372. Anal. Calcd for C18H29BrO3: C,
57.91; H, 7.83. Found: C, 57.69; H, 7.91.
(Z)-Methyl 3-bromo-2-(3-oxo-3-phenylpropyl)oct-2-enoate (3af):
1H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 7.6 Hz, 2H), 7.56 (t, J =
7.2 Hz, 1H), 7.46 (t, J = 7.6 Hz, 2H), 3.77 (s, 3H), 3.19 (t, J = 7.6 Hz,
2H), 2.91 (t, J = 8.0 Hz, 2H), 2.83 (t, J = 7.6 Hz, 2H), 1.67−1.60 (m,
2H), 1.36−1.26 (m, 4H), 0.91 (t, J = 6.4 Hz, 3H); 13C NMR (100
MHz, CDCl3) δ 198.9, 167.0, 142.7, 136.7, 133.1, 131.3, 128.6, 128.1,
52.1, 39.9, 36.7, 30.9, 29.7, 28.4, 22.4, 14.0 ppm; νmax(KBr)/cm−1
2952, 1721, 1443, 1260; MS (EI) m/z 41, 77, 91, 105, 227, 255, 287,
366. Anal. Calcd for C18H23BrO3: C, 58.86; H, 6.31. Found: C, 58.68;
H, 6.39.
(Z)-Ethyl 2-(bromo(phenyl)methylene)-5-oxoheptanoate (3cc).
1H NMR (400 MHz, CDCl3) δ 7.34−7.28 (m, 5H), 3.90 (q, J =
7.2 Hz, 2H), 2.92−2.87 (m, 2H), 2.77−2.73 (m, 2H), 2.49 (q, J = 7.2
Hz, 2H), 1.09 (t, J = 7.2 Hz, 3H), 0.84 (t, J = 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 209.8, 167.2, 140.7, 134.8, 132.4, 128.9, 128.1,
61.1, 39.8, 35.8, 29.6, 13.4, 7.8 ppm; νmax(KBr)/cm−1 2979, 1712,
1449, 1272; MS (EI) m/z 57, 105, 129, 157, 185, 259, 338. Anal. Calcd
for C16H19BrO3: C, 56.65; H, 5.65. Found: C, 56.48; H, 5.67.
(Z)-Methyl 2-(3-oxopentyl)-3-(2-phenylethynyl)oct-2-enoate
1
(4aca): H NMR (400 MHz, CDCl3) δ 7.47−7.44 (m, 2H), 7.36−
7.33 (m, 3H), 3.78 (s, 3H), 2.92−2.88 (m, 2H), 2.66−2.63 (m, 2H),
2.59−2.55 (m, 2H), 2.44 (q, J = 7.2 Hz, 2H), 1.68−1.62 (m, 2H),
1.37−1.33 (m, 4H), 1.06 (t, J = 7.2 Hz, 3H), 0.91 (t, J = 6.8 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 210.60, 168.37, 135.69, 134.13,
131.70, 128.83, 128.45, 122.78, 99.14, 88.46, 51.67, 41.47, 35.85,
33.85, 31.45, 28.54, 27.44, 22.49, 14.03, 7.86 ppm; νmax(KBr)/cm−1
2931, 2862, 1715, 1596, 1439, 1271, 1171, 1103, 1023, 757, 690;
HRMS EI (m/z) calcd for C22H28O3 340.2038, found 340.2033.
(Z)-Methyl 3-bromo-2-(2-methyl-3-oxo-3-phenylpropyl)oct-2-
1
enoate (3ag): H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 7.6 Hz,
2H), 7.56 (t, J = 7.2 Hz, 1H), 7.46 (t, J = 7.6 Hz, 2H), 3.73 (s, 3H),
2.97−2.92 (m, 1H), 2.83−2.68 (m, 3H), 1.62−1.55 (m, 2H), 1.33−
1.20 (m, 8H), 0.88 (t, J = 6.4 Hz, 3H); 13C NMR (100 MHz, CDCl3)
δ 203.1, 167.2, 142.4, 136.3, 133.0, 130.9, 128.6, 128.4, 52.0, 40.0, 39.6,
38.0, 30.8, 28.4, 22.4, 16.9, 13.9 ppm; νmax(KBr)/cm−1 2935, 1722,
1686, 1449, 1275, 1230; MS (EI) m/z 77, 105, 301, 380. Anal. Calcd
for C19H25BrO3: C, 59.85; H, 6.61. Found: C, 59.64; H, 6.68.
(Z)-Methyl 3-bromo-2-(3-(4-fluorophenyl)-3-oxopropyl)oct-2-
ASSOCIATED CONTENT
* Supporting Information
Spectral data for all new compounds; NOE studies on the
stereochemistry of 3aa. This material is available free of charge
■
S
1
enoate (3ah): H NMR (400 MHz, CDCl3) δ 8.03−7.99 (m, 2H),
AUTHOR INFORMATION
Corresponding Author
Notes
■
7.15−7.10 (m, 2H), 3.77 (s, 3H), 3.18−3.14 (m, 2H), 2.92−2.89 (m,
2H), 2.83 (t, J = 7.6 Hz, 2H), 1.67−1.59 (m, 2H), 1.36−1.29 (m, 4H),
0.91 (t, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 197.3, 166.9,
165.8 (d, 253 Hz), 142.8, 133.1 (d, 3 Hz), 131.2, 130.7 (d, 10 Hz),
115.7 (d, 22 Hz), 52.1, 39.9, 36.6, 30.9, 29.8, 28.4, 22.4, 14.0 ppm;
νmax(KBr)/cm−12943, 1719, 1597, 1236, 1159; MS (EI) m/z 41, 95,
123, 305, 384. Anal. Calcd for C18H22BrFO3: C, 56.11; H, 5.76. Found:
C, 55.94; H, 5.83.
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful to the National Natural Science Foundation of
China (20932002 and 21172076), National Basic Research
Program of China (973 Program) (2011CB808600), and
G u a n g d o n g N a t u r a l S c i e n c e F o u n d a t i o n
(10351064101000000) for financial support.
(Z)-Methyl 3-bromo-2-(3-(4-chlorophenyl)-3-oxopropyl)oct-2-
1
enoate (3ai): H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 8.8 Hz,
2H), 7.44 (d, J = 8.4 Hz, 2H), 3.77 (s, 3H), 3.17−3.13 (m, 2H), 2.91−
2.87 (m, 2H), 2.84−2.81 (m, 2H), 1.66−1.59 (m, 2H), 1.36−1.28 (m,
4H), 0.90 (t, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 197.7,
166.9, 142.9, 139.5, 135.0, 131.1, 129.5, 128.9, 52.1, 39.9, 36.7, 30.9,
29.7, 28.4, 22.4, 14.0 ppm; νmax(KBr)/cm−1 2949, 2363, 1720, 1257,
1091; MS (EI) m/z 111, 139, 321, 400. Anal. Calcd for C18H22BrClO3:
C, 53.82; H, 5.52. Found: C, 53.61; H, 5.56.
(Z)-Methyl 3-bromo-2-(3-oxo-3-p-tolylpropyl)oct-2-enoate (3aj):
1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.0 Hz, 2H), 7.26 (d, J =
8.0 Hz, 2H), 3.76 (s, 3H), 3.17−3.13 (m, 2H), 2.92−2.88 (m, 2H),
2.84−2.81 (m, 2H), 2.40 (s, 3H), 1.66−1.59 (m, 2H), 1.36−1.29 (m,
4H), 0.90 (t, J = 6.8 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 198.5,
167.0, 143.8, 142.5, 134.2, 131.4, 129.3, 128.2, 52.1, 39.9, 36.6, 30.9,
29.8, 28.4, 22.4, 21.6, 14.0 ppm; νmax(KBr)/cm−1 2953, 1721, 1609,
1441, 1260; MS (EI) m/z 91, 119, 301, 380. Anal. Calcd for
C19H25BrO3: C, 59.85; H, 6.61. Found: C, 59.73; H, 6.64.
REFERENCES
■
(1) (a) Tietze, L. F. Chem. Rev. 1996, 96, 115−136. (b) Shi, Z.; Ding,
S.; Cui, Y.; Jiao, N. Angew. Chem., Int. Ed. 2009, 48, 7895−7898.
(c) Zeni, G.; Larock, R. C. Chem. Rev. 2004, 104, 2285−2310.
(d) Arai, S.; Sato, T.; Koike, Y.; Hayashi, M.; Nishida, A. Angew. Chem.,
Int. Ed. 2009, 48, 4528−4531. (e) Hassan, J.; Svignon, M.; Gozzi, C.;
Schulz, E.; Lemaire, M. Chem. Rev. 2002, 102, 1359−1407. (f) Corbet,
J.; Mignani, G. Chem. Rev. 2006, 106, 2651−2710. (g) Li, C. Chem.
Rev. 2005, 105, 3095−3166. (h) Sakai, N.; Komatsu, R.; Uchida, N.;
Ikeda, R.; Konakahara, T. Org. Lett. 2010, 12, 1300−1303.
(2) For intramolecular nucleopalladation reactions, see: (a) Zhao, L.;
Lu, X. Angew. Chem., Int. Ed. 2002, 41, 4343−4345. (b) Zhang, Q.; Xu,
W.; Lu, X. J. Org. Chem. 2005, 70, 1505−1507. (c) Zhu, G.; Lu, X.
Organometallics 1995, 14, 4899−4904. (d) Zhang, Z.; Lu, X.; Xu, Z.;
Zhang, Q.; Han, X. Organometallics 2001, 20, 3724−3728. (e) Yin, G.;
Liu, G. Angew. Chem., Int. Ed. 2008, 47, 5442−5445. (f) Li, Y.; Jardine,
K. J.; Tan, R.; Song, D.; Dong, V. M. Angew. Chem., Int. Ed. 2009, 48,
(Z)-Methyl 3-bromo-2-(3-(4-methoxyphenyl)-3-oxopropyl)oct-2-
1
enoate (3ak): H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 8.8 Hz,
2H), 6.92 (d, J = 8.8 Hz, 2H), 3.87 (s, 3H), 3.77 (s, 3H), 3.15−3.11
(m, 2H), 2.91−2.81 (m, 4H), 1.67−1.59 (m, 2H), 1.35−1.28 (m, 4H),
0.91 (t, J = 6.8 Hz, 3H); 13C NMR (100 MHz, CDCl3) δ 197.5, 167.0,
163.5, 142.4, 131.5, 130.4, 129.8, 113.7, 55.5, 52.1, 39.9, 36.4, 30.9,
2033
dx.doi.org/10.1021/jo202416h | J. Org. Chem. 2012, 77, 2029−2034