2
7
931, 2816, 2772, 1597, 1480, 1462, 1229, 1092, 927, 820 and
References
49; δ (400 MHz; CDCl ; Me Si) 1.32 (3 H, d, J 6.8, Me), 2.11
H
3
4
1
For example, (a) Organoselenium Chemistry, ed. D. Liotta, Wiley,
New York, 1987, p. 127; (b) C. Paulmier, Selenium Reagents and
Intermediates in Organic Synthesis, Pergamon Press, Oxford, 1986;
(c) The chemistry of organic selenium and tellurium compounds,
vol. 1, ed. S. Patai and Z. Rappoport and vol. 2, ed. S. Patai, Wiley,
New York, 1986 and 1987.
(
6 H, s, NMe ), 2.83–3.15 (2 H, m, CH ), 3.20–3.39 (2 H, m,
2
2
SeCH ), 4.00 (1 H, q, J 6.8, CH), 4.09 (5 H, s, Fc), 4.31 (3 H, br
s, Fc) and 4.90 (1 H, m, OCH), 6.71–6.83 (2 H, m, Ar) and
2
ϩ
7
.04–7.24 (2 H, m, Ar); m/z (FAB HRMS) 469.0602 (M ,
C H FeNOSe requires 469.0609); m/z (FAB LRMS) 469
23
ϩ
27
2 K. Hiroi and S. Sato, Synthesis, 1985, 635.
(
M ).
3
C. Paulmier, F. Outurquin and J.-C. Plaquevent, Tetrahedron Lett.,
988, 29, 5889.
(a) S. Tomoda, K. Fujita and M. Iwaoka, Phosphorus Sulfur Silicon
Relat. Elem., 1992, 67, 247; (b) S. Tomoda, K. Fujita and M.
Iwaoka, Chem. Lett., 1992, 1123; (c) S. Tomoda, K. Fujita and
M. Iwaoka, J. Chem. Soc., Chem. Commun., 1990, 129; (d) S.
Tomoda and M. Iwaoka, Chem. Lett., 1988, 1895.
1
3
-{2-[1-(Dimethylamino)ethyl]ferrocenylseleno}-2-ethyltetra-
4
Ϫ1
hydrofuran 6e. A brown oil; 89% yield; νmax/cm 2968, 2933,
2
Me Si) 0.83 (3 H, t, J 7.3, Me), 1.30 (3 H, d, J 6.8, Me), 1.43–
1
m, CHH), 2.11 (6 H, s, NMe ), 2.21–2.27 (1 H, m, SeCH), 3.76–
3
J 6.8, CH), 4.09 (5 H, s, Fc), 4.21 (2 H, s, Fc) and 4.34 (1 H, s,
Fc); m/z (FAB HRMS) 435.0771 (M , C H FeNOSe requires
8
7
2
,
2
8
5
4
,
2
8
1
5
,
2
7
7
3
,
1
0
9
2
a
n
d
9
2
7
;
δ
(
2
7
0
M
H
z
;
C
D
C
l
;
H
3
4
.52 (2 H, m, CH ), 1.90–1.96 (1 H, m, CHH), 2.02–2.10 (1 H,
2
5
6
H. J. Reich and K. E. Yelm, J. Org. Chem., 1991, 56, 5672.
2
(a) R. Déziel, E. Malenfant, C. Thibault, S. Fréchette and
M. Gravel, Tetrahedron Lett., 1997, 38, 4753; (b) R. Déziel
and E. Malenfant, J. Org. Chem., 1996, 61, 1875; (c) R. Déziel and
E. Malenfant, J. Org. Chem., 1995, 60, 4660; (d) R. Déziel,
S. Goulet, L. Grenie, J. Bordelean and J. Bernier, J. Org. Chem.,
.86 (2 H, m, OCH ), 3.76–3.86 (1 H, m, OCH), 3.99 (1 H, q,
2
ϩ
20
29
ϩ
4
35.0766); m/z (FAB LRMS) 435 (M ).
1
993, 58, 3619.
7 (a) K. Fujita, K. Murata, M. Iwaoka and S. Tomoda, Tetrahedron,
997, 53, 2029; (b) K. Fujita, K. Murata, M. Iwaoka and S.
N-Ethoxycarbonyl-2-{2-[1-(dimethylamino)ethyl]ferrocenyl-
1
selenomethyl}pyrrolidine 8a. A brown oil; 77% yield (Found:
C, 54.20; H, 6.99; N, 4.96. C H FeN O Se requires C, 54.67;
Tomoda, Tetrahedron Lett., 1995, 36, 5219; (c) K. Fujita, K.
Murata, M. Iwaoka and S. Tomoda, J. Chem. Soc., Chem.
Commun., 1995, 1641; (d) K. Fujita, M. Iwaoka and S. Tomoda,
Chem. Lett., 1994, 923.
22
32
2
2
Ϫ1
H, 6.78; N, 5.54%); νmax/cm 2966, 1729 (C᎐O), 1167 and 1090;
δ (270 MHz; CDCl ; Me Si) 1.28 (3 H, t, J 7.3, Me), 1.23 (2 H,
H
3
4
m, CH ), 1.33 (3 H, d, J 6.9, Me), 1.73–1.84 (2 H, m, CH ), 2.10
8 (a) T. G. Back and B. P. Dyck, Chem. Commun., 1996, 2527; (b)
T. G. Back, B. P. Dyck and M. Parvez, J. Org. Chem., 1995, 60, 703.
2
2
(
6 H, s, NMe ), 2.76–2.99 (2 H, m, SeCH ), 3.99 (1 H, q, J 6.9,
2
2
9
(a) G. Fragale, M. Neuburger and T. Wirth, Chem. Commun., 1998,
CH), 4.08 (5 H, s, Fc), 4.18 (3 H, br, Fc), 4.18 (2 H, q, J 7.3, CH2
of Et group) and 4.30 (3 H, m); m/z (FAB HRMS) 492.0972
1867; (b) T. Wirth, G. Fragale and M. Spichty, J. Am. Chem. Soc.,
998, 120, 3376; (c) T. Wirth, Liebigs Ann./Recl., 1997, 2189 and
1
ϩ
(
M , C H FeN O Se requires 492.0981); m/z (FAB LRMS)
2
2
32
2
2
references cited therein; (d) T. Wirth, Angew. Chem., Int. Ed. Engl.,
995, 34, 1726.
ϩ
4
92 (M ).
1
1
0 (a) S. Fukuzawa, Y. Kasugahara and S. Uemura, Tetrahedron Lett.,
1994, 35, 9403; (b) S. Fukuzawa, K. Takahashi, H. Kato and
H. Yamazaki, J. Org. Chem., 1997, 62, 7711.
N-Ethoxycarbonyl-2-{2-[1-(dimethylamino)ethyl]ferrocenyl-
selenomethyl}-4,4-dimethylpyrrolidine 8b. A brown oil; 3% yield;
νmax/cm 2968, 1722 (C᎐O), 1090 and 933; δH (270 MHz;
CDCl ; Me Si) 1.05 (6 H, s, 2 × Me), 1.28 (3 H, t, J 7.3, Me),
1
Ϫ1
11 M. Tiecco, L. Testaferri, C. Santi, F. Marini, L. Bagnoli and
A. Temperini, Tetrahedron Lett., 1998, 39, 2809.
2 Y. Nishibayashi, S. K. Srivastava, H. Takada, S. Fukuzawa and
3
4
1
.32 (3 H, d, J 6.9, Me), 1.76–1.87 (2 H, m, CH ), 2.12 (6 H, s,
2
S. Uemura, J. Chem. Soc., Chem. Commun., 1995, 2321.
NMe ), 2.75–3.03 (2 H, m, SeCH ), 3.99 (1 H, q, J 6.9, CH),
2
2
13 (a) Y. Nishibayashi, J. D. Singh, S. Fukuzawa and S. Uemura, J. Org.
Chem., 1995, 60, 4114; (b) Y. Nishibayashi, J. D. Singh, S. Uemura
and S. Fukuzawa, Tetrahedron Lett., 1994, 35, 3115.
4
4
5
.08 (5 H, s, Fc), 4.18 (3 H, br, Fc), 4.20 (2 H, q, J 7.3, CH ) and
2
.20 (3 H containing CH of Et group, m); m/z (FAB LRMS)
20 (M ).
2
ϩ
14 (a) Y. Nishibayashi and S. Uemura, Rev. Heteroatom. Chem., 1996,
1
4, 83; (b) Y. Nishibayashi, J. D. Singh, Y. Arikawa, S. Uemura and
M. Hidai, J. Organometal. Chem., 1997, 531, 13; (c) Y. Nishibayashi,
K. Segawa, J. D. Singh, S. Fukuzawa, K. Ohe and S. Uemura,
Organometallics, 1996, 15, 370; (d) Y. Nishibayashi, J. D. Singh,
K. Segawa, S. Fukuzawa and S. Uemura, J. Chem. Soc., Chem.
Commun., 1994, 1375.
N-Ethoxycarbonyl-2,3-dihydro-2-{2-[1-(dimethylamino)ethyl]-
ferrocenylselenomethyl}indole 8c. A brown oil; 3% yield; νmax/
Ϫ1
cm 2969, 1724 (C᎐O), 1090 and 932; δH (270 MHz; CDCl3;
Me Si) 1.06 (3 H, t, J 7.3, Me), 1.32 (3 H, d, J 6.8, Me), 2.13
4
(
6 H, s, NMe ), 2.56–3.11 (2 H, m, CH ), 3.18–3.38 (2 H, m,
15 G. Mugesh, A. Panda, H. B. Singh, N. S. Punekar and R. J. Butcher,
Chem. Commun., 1998, 2227.
2
2
SeCH ), 4.00 (1 H, q, J 6.8, CH), 4.08 (5 H, s, Fc), 4.20 (3 H
containing CH of Et group, m), 4.31 (3 H, br s, Fc), 6.70–6.83
2
1
6 For review, see for example: K. E. Harding and T. H. Tiner,
Comprehensive Organic Synthesis, ed. B. M. Trost and I. Fleming,
Pergamon Press, Oxford, 1991, vol. 4, ch. 1.9.
2
(
2 H, m, Ar) and 7.04–7.27 (2 H, m, Ar); m/z (FAB HRMS)
ϩ
5
04.0998 (M , C H FeN O Se requires 504.0991); m/z (FAB
26 32 2 2
ϩ
17 (a) D. L. J. Clive, G. Chittattu, N. J. Curtis, W. A. Kiel and
C. K. Wong, J. Chem. Soc., Chem. Commun., 1977, 725; (b) D. L. J.
Clive, C. G. Russell, G. Chittattu and A. Singh, Tetrahedron, 1980,
36, 1399; (c) D. L. J. Clive, G. Chittattu, V. Farina, A. Singh, C. K.
Wong, W. A. Kiel and S. M. Menchen, J. Org. Chem., 1980, 45, 2120;
LRMS) 504 (M ).
N-Ethoxycarbonyl-2-{2-[1-(dimethylamino)ethyl]ferrocenyl-
selenomethyl}piperidine 8d. A brown oil; 53% yield (Found: C,
5
6
and 927; δ (270 MHz; CDCl ; Me Si) 1.28 (3 H, t, J 7.3, Me),
1
(
d) K. C. Nicolaou and Z. Lysenko, Tetrahedron Lett., 1977, 1257;
3.65; H, 6.68; N, 5.43. C H FeN O Se requires C, 53.78; H,
23 34 2 2
Ϫ1
(e) K. C. Nicolaou, Tetrahedron, 1981, 37, 4097.
.56; N, 5.7%); νmax/cm 2968, 2931, 2872, 1721 (C᎐O), 1092
1
8 Here R of (R,S) shows the absolute configuration at the carbon of
the 1-(dimethylamino)ethyl moiety, while S of (R,S) shows the
configuration around the ferrocene axis.
H
3
4
.23 (4 H, m, 2 × CH ), 1.33 (3 H, d, J 6.9, Me), 1.73–1.84 (2 H,
2
m, CH ), 2.10 (6 H, s, NMe ), 2.76–2.99 (2 H, m, SeCH ), 3.99
19 The isolated yield of (S)-9 (γ-valerolactone) was low (~20%), but its
2
2
2
25
optical rotation observed {[α] Ϫ25.8 (c 0.5, CHCl )} clearly showed
(
(
1 H, q, J 6.9, CH), 4.08 (5 H, s, Fc), 4.18 (3 H, br, Fc), 4.18
D
3
its S configuration (ref. 20).
20 (a) T. Hafner and H. U. Reibig, Liebigs Ann. Chem. 1989, 937;
b) K. Mori, Tetrahedron, 1975, 31, 3011.
2 H, q, J 7.3, CH of Et group) and 4.30 (3 H, m); m/z (FAB
2
ϩ
LRMS) 506 (M ).
(
2
2
2
1 G. Gokei and I. Ugi, J. Chem. Educ., 1972, 49, 82.
2 R. G. Salomon and S. Ghosh, Org. Synth., 1984, 62, 125.
3 M. R. Gagné, C. L. Stern and T. J. Marks, J. Am. Chem. Soc., 1992,
114, 275.
Acknowledgements
The present work was partly supported by a Grant-in-Aid for
Scientific Research from the Ministry of Education, Science,
Culture, and Sports, Japan. H. T. gratefully acknowledges a
Fellowship from the Japan Society for the Promotion of
Science for Japanese Junior Scientists.
2
4 K. Maruyama, T. Ogawa, Y. Kubo and T. Araki, J. Chem. Soc.,
Perkin Trans. 1, 1985, 2025.
Paper 9/01087D
1
516
J. Chem. Soc., Perkin Trans. 1, 1999, 1511–1516