Anionic Bridged Bis(amidinate) Lithium Lanthanide Complexes
FULL PAPERS
General Procedure for the Synthesis of Complexes
General Procedure for the Synthesis of Amides from
the Reaction of Pyrrolidine with Benzyl Benzoate
Catalyzed by Complex I and V (Taking I as an
Example)
[
[
Li
Li
ACHTUNGTRENNUNG( DME) ] ACHTUNGTRENNUNG[ LnL ](Ln=Nd, Eu) (Taking
ACHTUNGTRENNUNG( DME) ] ACHTUNGTRENNUNG[ NdL ] (IV) as an Example)
3 2
3 2
A stirred suspension of NdCl (0.37 g, 1.5 mmol) in THF
3
(
20 mL) was treated with LLi
A
H
U
G
R
N
U
G
A 30-mL of Schlenk flask was charged with the solution of
complex I (2.00 mL, 0.02 mmol). pyrrolidine was added
(0.08 mL, 1.00 mmol), after stirring for 0.5 h, benzyl ben-
zoate was then added (0.18 mL, 1.00 mmol). The resulting
mixture was stirred at 258C for 3 h, filtered through a small
plug of silica gel to remove the catalyst. The crude product
was purified by column chromatography: (ethyl acetate:
petroleum ether=1:3); yield: 18 mg (10%).
2
0.5
THF (15 mL). The reaction mixture was stirred at room
temperature for 48 h, and the solvent was removed under
vacuum. The residue was extracted with toluene (40 mL)
and the volume of the extract was reduced to 10 mL fol-
lowed by an addition of DME (1 mL). Cooling to 08C af-
forded IV as light-blue crystals; yield: 1.14 g (60%): mp
1
(
(
86–1898C. IR (KBr pellet): n=2961 (m), 1625 (m), 1540
m), 1487 (m), 1446 (m), 1374 (m), 1250 (w), 1190 (w), 980
w), 903 (w), 833 (w), 779 (w), 700 cm (m); anal. calcd. for
C H LiN O Si Nd (MW: 1266.98): C 54.98, H 7.80, N 8.84,
58
98
8
6
4
Nd 11.38%; found: C 54.04, H 7.35, N 9.47, Nd 11.54%. Acknowledgements
Monoclinic, P31 a=15.7981(11) ꢂ, b=15.7981(11) ꢂ, c=
3
2
4.2228(19) ꢂ, a=908, b=908, g=1208, V=5235.6(7) ꢂ ,
We are grateful to the National Natural Science Foundation
of China (Grant no. 20632040) for financial support.
À3
Z=3, D =1.206 gcm , 12717 independent reflections. R=
x
0.0723 and wR was 0.1873.
2
General Procedure for the Synthesis of Complex
Nd L (VII)
References
2
3
[
1] a) M. Shibasaki, N. Yoshikawa, Chem. Rev. 2002, 102,
187–2209; b) S. Kobayashi, M. Sugiura, H. Kitagawa,
A solution of LLi2 ACHTUNGTRENNUNG( THF) (1.41 g, 3 mmol) in THF (30 mL)
0.5
2
was added to a stirring suspension of NdCl (0.50 g, 2 mmol)
3
W. W. L. Lam, Chem. Rev. 2002, 102, 2227–2302.
2] For general reviews, including hydroamination, see:
a) S. Hong, T. J. Marks, Acc. Chem. Res. 2004, 37, 673–
in THF (25 mL). Complex VII was obtained as blue crystals
[
[18]
by the published procedure; yield: 0.79 g (48%). IR (KBr
pellet): n=2958 (m), 1633 (m), 1601 (m), 1537 (m), 1383
6
86; b) H. C. Aspinall, Chem. Rev. 2002, 1807–1850;
(
7
m), 1210 (w), 1058 (w), 890 (w), 839 (w), 781 (w), 756 (w),
c) F. T. Edelmann, D. M. M. Freckmann, H. Schumann,
Chem. Rev. 2002, 1851–1896; d) S. Arndt, J. Okuda,
Chem. Rev. 2002, 102, 1953–1976; e) G. A. Molander,
J. A. C. Romero, Chem. Rev. 2002, 102, 2161–2185;
f) Topics in Organometallic Chemistry, (Ed.: S. Kobaya-
shi), Springer, Berlin, 1999, Vol. 2.
À1
00 cm (m); anal. calcd. for C H N O Si Nd (MW:
7
3
112 12
2
6
2
1646.74): C 53.24, H 6.86, N 10.21, Nd 17.52; found: C 53.77,
H 7.26, N 9.87, Nd 17.04%.
General Procedure for the Synthesis of Amides from
the Reaction of Aldehydes with Amines Catalyzed by
Complex I (Product N-Benzyl-N-methylbenzamide
[
[
[
[
[
3] Q. Li, S. Wang, S. Zhou, G. Yang, X. Zhu, Y. Liu, J.
Org. Chem. 2007, 72, 6763–6767.
4] D. Cui, M. Nishiura, Z. Hou, Angew. Chem. 2005, 117,
3aa as an Example)
9
81–984; Angew. Chem. Int. Ed. 2005, 44, 959–962.
5] J. Wang, F. Xu, T. Cai, Q. Shen, Org. Lett. 2008, 10,
45–448.
A 30-mL of Schlenk flask was charged with the solution of
complex I (2.00 mL, 0.02 mmol). N-Methylbenzylamine was
added (0.13 mL, 1.00 mmol), after stirring for 0.5 h, benzal-
dehyde was then added (0.3 mL, 3.00 mmol). The resulting
mixture was stirred at 258C for 3 h, filtered through a small
plug of silica gel to remove the catalyst. The crude product
was purified by column chromatography: (ethyl acetate:
petroleum ether=1:5); yield: 216 mg (98%).
4
6] K. Komeyama, D. Sasayama, T. Kawabata, K. Take-
hira, K. Takaki, J. Org. Chem. 2005, 70, 10679–10687.
7] M. Sugita, A. Yamaguchi, N. Yamagiwa, S. Handa, S.
Matsunaga, M. Shibasaki, Org. Lett. 2005, 7, 5339–
5
342.
8] Q. Shen, W. Huang, J. Wang, X. Zhou, Organometallics
008, 27, 301–303.
9] J. M. Humphrey, A. R. Chanberlin, Chem. Rev. 1997,
97, 2243–2266.
[
[
2
General Procedure for the Synthesis of Benzyl
Benzoate from the Reaction of Benzaldehyde
Catalyzed by Complex I and V (Taking I as an
Example)
[
10] a) R. S. Davidson, J. Edwards, S. K. Warburton, J.
Chem. Soc. Perkin Trans. 1 1976, 1511–1514; b) I. E.
Marko, A. Mekhalfia, Tetrahedron Lett. 1990, 31, 7237–
7
240.
A 30-mL of Schlenk flask was charged with the solution of
complex I (2.00 mL, 0.02 mmol). Benzaldehyde was then
added (0.2 mL, 2.00 mmol). The resulting mixture was
stirred at 258C for 3 h, filtered through a small plug of silica
gel to remove the catalyst. The crude product was purified
by column chromatography: (ethyl acetate:petroleum
ether=1:10); yield: 78 mg (37%).
[11] K. Ishihara, T. Yano, Org. Lett. 2004, 6, 1983–1986.
[12] L. Zhang, S. Wang, S. Zhou, G. Yang, E. Sheng, J. Org.
Chem. 2006, 71, 3149–3153.
[13] a) K. Nakagawa, H. Onoue, K. Minami, J. Chem. Soc.
Chem. Commun. 1966, 17–18; b) Y. Tamaru, Y.
Yamada, Z. Yoshida, Synthesis 1983, 474–476; c) T.
Naota, S. Murahashi, Synlett 1991, 693–694; d) A. Till-
Adv. Synth. Catal. 2009, 351, 1363 – 1370
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1369