442
N. Tsukada et al. / Journal of Organometallic Chemistry 687 (2003) 436ꢀ443
/
0.5 mmHg). The 31P{1H}-NMR spectra (162 MHz,
CDCl3) of the resulted pale-yellow oil exhibited two
singlets at 21.81 and 38.35 ppm.
Hz, 1H), 7.83 (d, Jꢄ
/
3.8 Hz, 1H), 7.18 (t, Jꢄ
/
3.8 Hz,
1H), 3.43 (q, Jꢄ7.2 Hz, 4H), 1.25 (t, Jꢄ
/
/7.2 Hz, 6H).
4.4.6. N,N-Diethyl-2-thiophenylglyoxamide
Isolated by column chromatography (hexane/ethyl
acetateꢄ
1/1). Yellow oil. 1H-NMR (CDCl3): d 8.18
(dd, Jꢄ2.9, 1.2 Hz, 1H), 7.58 (dd, Jꢄ5.2, 1.2 Hz, 1H),
7.36 (dd, Jꢄ5.2, 2.9 Hz, 1H), 3.53 (q, Jꢄ7.1 Hz, 2H),
3.28 (q, Jꢄ7.1 Hz, 2H), 1.27 (t, Jꢄ7.1 Hz, 3H), 1.18 (t,
Jꢄ
7.1 Hz, 3H); 13C-NMR (CDCl3): d 185.1, 166.5,
138.7, 136.1, 127.0, 126.9, 42.2, 39.0, 14.2, 12.7. IR
(neat): 1669, 1638, 1240, 1140 cmꢃ1; GCMS (70 eV) m/
z 111 (52), 100 (72), 72 (100), 44 (37), 39 (49); Anal.
Calc. for C10H13NO2S: C, 56.85; H, 6.20; N, 6.63; S,
15.18. Found: C, 56.58; H, 6.08; N, 6.33; S, 15.25%.
4.4.1. N,N-Diethyl-4-nitrophenylglyoxamide
Isolated by column chromatography (hexane/ethyl
/
acetateꢄ
1H-NMR (CDCl3): d 8.35 (dt, Jꢄ
8.13 (dt, Jꢄ9.0, 2.0 Hz, 2H), 3.58 (q, Jꢄ
3.27 (q, Jꢄ7.1 Hz, 2H), 1.31 (t, Jꢄ7.1 Hz, 3H), 1.19 (t,
Jꢄ
7.1 Hz, 3H); 13C-NMR (CDCl3): d 189.1, 165.4,
/
1/1). A light orange solid: m.p. 95ꢀ
9.0, 2.0 Hz, 2H),
7.1 Hz, 2H),
/
96 8C.
/
/
/
/
/
/
/
/
/
/
/
/
/
151.0, 137.7, 130.7, 124.1, 119.6, 42.2, 39.2, 14.2, 12.8;
IR (KBr): 1686, 1638, 1524, 1347, 1224 cmꢃ1; GCMS
(70 eV) m/z 100 (100), 72 (87), 44 (39); Anal. Calc. for
C12H14N2O4: C, 57.59; H, 5.64; N, 11.19. Found: C,
57.44; H, 5.63; N, 11.14%.
4.4.2. N,N-Diethyl-1-naphthylglyoxamide
Isolated by column chromatography (hexane/ethyl
References
acetateꢄ
(CDCl3): d 9.26 (d, Jꢄ
1H), 7.99 (d, Jꢄ7.7 Hz, 1H), 7.89 (d, Jꢄ
7.67 (t, Jꢄ7.7 Hz, 1H), 7.57 (t, Jꢄ7.7 Hz, 1H), 7.52 (d,
Jꢄ7.7 Hz, 1H), 3.56 (q, Jꢄ7.1 Hz, 2H), 3.29 (q, Jꢄ7.1
Hz, 2H), 1.30 (t, Jꢄ7.1 Hz, 3H), 1.15 (t, Jꢄ7.1 Hz,
/
2/1). A red solid: m.p. 43ꢀ
7.7 Hz, 1H), 8.08 (d, Jꢄ
7.7 Hz, 1H),
/
44 8C. 1H-NMR
/
/7.7 Hz,
[1] (a) A. Yamamoto, Bull. Chem. Soc. Jpn. 68 (1995) 433;
(b) F. Ozawa, T. Yamamoto, A. Yamamoto, Synth. Org. Chem.
Jpn. 43 (1985) 442.
/
/
/
/
[2] F. Ozawa, H. Soyama, T. Yamamoto, A. Yamamoto, Tetrahe-
dron Lett. (1982) 3383.
/
/
/
/
/
[3] T. Kobayashi, M. Tanaka, J. Organomet. Chem. 233 (1982) C64.
[4] (a) F. Ozawa, T. Sugimoto, Y. Yuasa, M. Santra, T. Yamamoto,
A. Yamamoto, Organometallics 3 (1984) 683;
(b) F. Ozawa, H. Soyama, H. Yanagihara, I. Aoyama, H. Takino,
K. Izawa, T. Yamamoto, A. Yamamoto, J. Am. Chem. Soc. 107
(1985) 3235;
3H); 13C-NMR (CDCl3): d 194.0, 167.1, 135.6, 134.2,
133.9, 130.9, 129.1, 128.6, 128.5, 126.8, 125.7, 124.4,
42.1, 38.7, 13.8, 12.7; IR (KBr): 1670, 1639, 1230, 784
cmꢃ1; GCMS (70 eV) m/z 255 (17), 155 (100), 127 (53),
100 (26), 72 (27); Anal. Calc. for C16H17NO2: C, 75.27;
H, 6.71; N, 5.49. Found: C, 75.24; H, 6.88; N, 5.44%.
(c) T. Son, H. Yanagihara, F. Ozawa, A. Yamamoto, Bull. Chem.
Soc. Jpn. 61 (1988) 1251.
[5] H. Urata, Y. Ishii, T. Fuchikami, Tetrahedron Lett. 30 (1989)
4407.
4.4.3. N,N-Diethyl-2-naphthylglyoxamide
Isolated by column chromatography (hexane/ethyl
[6] S.C. Bonnaire, J. Carpentier, Y. Castanet, A. Mortreux, Tetra-
hedron Lett. 40 (1999) 3717.
1
acetateꢄ
/
2/1). A white solid: m.p. 52ꢀ
/
53 8C. H-NMR
[7] (a) F. Ozawa, N. Kawasaki, T. Yamamoto, A. Yamamoto,
Chem. Lett. (1985) 567;
(CDCl3): d 8.43 (s, 1H), 8.04-7.86 (m, 4H), 3.62 (q, Jꢄ
7.2 Hz, 2H), 3.28 (q, Jꢄ7.2 Hz, 2H), 1.33 (t, Jꢄ7.2 Hz,
3H), 1.16 (t, Jꢄ
7.2 Hz, 3H); 13C-NMR (CDCl3): d
/
(b) F. Ozawa, N. Kawasaki, H. Okamoto, T. Yamamoto, A.
Yamamoto, Organometallics 6 (1987) 1640.
[8] T. Sakakura, H. Yamashita, T. Kobayashi, T. Hayashi, M.
Tanaka, J. Org. Chem. 52 (1987) 5733.
/
/
/
191.6, 166.8, 136.2, 132.7, 132.4, 130.6, 129.8, 129.2,
128.9, 127.9, 127.0, 123.7, 42.1, 38.8, 14.1, 12.8; IR
(KBr): 1674, 1643, 1461, 1190, 1119, 786 cmꢃ1; GCMS
(70 eV) m/z 255 (7), 155 (100), 127 (61), 100 (35), 72
(37); Anal. Calc. for C16H17NO2: C, 75.27; H, 6.71; N,
5.49. Found: C, 75.16; H, 6.84; N, 5.45%.
[9] M. Tanaka, T. Kobayashi, T. Sakakura, J. Chem. Soc. Chem.
Commun. (1985) 837.
[10] T. Kobayashi, T. Sakakura, M. Tanaka, Tetrahedron Lett. 28
(1987) 2721.
[11] S.C. Bonnaire, J. Carpentier, A. Mortreux, Y. Castanet, Adv.
Synth. Catal. 5 (2001) 343.
[12] Y. Lin, H. Alper, Angew. Chem. Int. Ed. 40 (2001) 779.
[13] (a) F. Ozawa, H. Yanagihara, A. Yamamoto, J. Org. Chem. 51
(1986) 415;
4.4.4. N,N-Diethyl-3-pyridylglyoxamide
Isolated by column chromatography (hexane/ethyl
1
(b) F. Ozawa, I. Yamagami, M. Nakano, F. Fujisawa, A.
Yamamoto, Chem. Lett. (1989) 125.
acetateꢄ
/
10/1). H-NMR (CDCl3): d 9.15 (d, Jꢄ
/
1.9
7.9,
7.9, 4.8 Hz, 1H), 3.59 (q, Jꢄ
7.1 Hz, 2H), 1.32 (t, Jꢄ7.1 Hz,
7.1 Hz, 3H).
Hz, 1H), 8.87 (dd, Jꢄ
1.9 Hz, 1H), 7.51 (dd, Jꢄ
7.1 Hz, 2H), 3.30 (q, Jꢄ
3H), 1.21 (t, Jꢄ
/
4.8, 1.9 Hz, 1H), 8.27 (dt, Jꢄ
/
[14] N. Tsukada, O. Tamura, Y. Inoue, Organometallics 21 (2002)
2521.
/
/
/
/
[15] N.D. Jones, B.R. James, Adv. Synth. Catal. 344 (2002) 1126.
[16] G.P. Abramo, L. Li, T.J. Marks, J. Am. Chem. Soc. 124 (2002)
13966.
/
[17] Y. Inada, Y. Nishibayashi, M. Hidai, S. Uemura, J. Am. Chem.
Soc. 124 (2002) 15172.
4.4.5. N,N-Diethyl-2-thiophenylglyoxamide
Isolated by column chromatography (hexane/ethyl
acetateꢄ 3.8
2/1). 1H-NMR (CDCl3): d 8.41 (d, Jꢄ
[18] M.E. Broussard, B. Juma, S.G. Train, G.G. Stanley, Science 260
(1993) 1784.
/
/