Chiral Imidazolinium Carbene from a Carbohydrate and Its RhI Complex
N,NЈ-Bis(methyl 4,6-O-benzylidene-3-deoxy-α- -altropyrano-3-yl)-
FULL PAPER
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 165.28, 137.38, 137.07,
129.17, 128.36, 128.29, 126.46, 126.31, 126.08, 102.51, 102.33,
102.03, 101.88, 77.40, 75.80, 69.88, 69.68, 69.49, 69.08, 61.74,
D
1,2-diaminoethane (3): A mixture of methyl 2,3-anhydro-4,6-O-
benzylidene-α--mannopyranoside (1; 4.1 g, 15.5 mmol) and eth-
ane-1,2-diamine (0.4 g, 6.67 mmol) in methanol (60 mL) was
stirred in an autoclave at 140 °C for 12 h. After cooling the reaction
mixture, the solvent was evaporated, and the residue was purified
by chromatography (3–10% methanol in dichloromethane) to af-
ford the product. Yield: 3.4 g (86%). M.p. 91–93 °C. [α]2D1 = +112.2
(c = 1.0, ethanol). 1H NMR (400 MHz, CDCl3): δ = 7.50–7.30 (m,
10 H), 5.47 (s, 2 H), 4.52 (s, 2 H), 4.30–4.25 (m, 2 H), 4.10–4.00
(m, 2 H), 3.95–3.90 (m, 2 H), 3.91 (br., 2 H), 3.80–3.70 (m, 2 H),
3.34 (s, 6 H), 3.22 (br., 2 H), 3.10–3.05 (m, 2 H), 2.90–2.85 (m, 2
H), 2.65–2.55 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
137.64 129.06 128.38 (2 C), 126.21 (2 C), 102.05 (2 C), 77.86, 70.80,
59.55, 58.92, 58.66, 55.60, 55.54, 47.16, 45.51 ppm. IR (KBr): ν =
˜
3409, 3257, 2934, 1654, 1455, 1380, 1136, 1107, 1049, 974, 756,
700 cm–1. MS (ESI): m/z (%) = 617 (20) [M + 1]+.
Supporting Information (see footnote on the first page of this arti-
cle): Full characterization of compounds 3–6.
Acknowledgments
This work was financially supported by the National Natural Sci-
ence Foundation of China (20473089), the National Basic Research
Program of China (2003CB61615803), and Fujian Normal Univer-
sity.
69.50, 58.69, 57.10, 55.47, 47.08, 46.11 ppm. IR (KBr): ν = 3440,
˜
2907, 1637, 1457, 1380, 1105, 1067, 1044, 974, 755, 670 cm–1. MS
(ES): m/z (%) = 589 (100) [M + 1]+.
N,NЈ-1,3-Bis(methyl 4,6-O-benzylidene-3-deoxy-α-D-altropyrano-3-
[1] a) A. J. Arduengo III, R. L. Harlow, M. Kline, J. Am. Chem.
Soc. 1991, 113, 361; b) A. J. Arduengo III, Acc. Chem. Res.
1999, 32, 913; c) W. A. Herrmann, C. Köcher, Angew. Chem.
Int. Ed. Engl. 1997, 36, 2162.
[2] a) W. A. Herrmann, Angew. Chem. Int. Ed. 2002, 41, 1290; b)
M. C. Perry, K. Burgess, Tetrahedron: Asymmetry 2003, 14,
951.
[3] D. Enders, T. Balensiefer, Acc. Chem. Res. 2004, 37, 534.
[4] a) J. Huang, H.-J. Schanz, E. D. Stevens, S. P. Nolan, Organo-
metallics 1999, 18, 2370; b) W. A. Herrmann, M. Elison, J. Fi-
scher, C. Köcher, G. R. J. Artus, Angew. Chem. Int. Ed. Engl.
1995, 34, 2371; c) P. Bazinet, G. P. A. Yap, D. S. Richeson, J.
Am. Chem. Soc. 2003, 125, 13314.
[5] a) H. Yu, J.-C. Shi, H. Zhang, P. Yang, X. Wang, Z. Jin, J.
Mol. Catal. A 2006, 250, 15; b) J.-C. Shi, P. Yang, Q. Tong, Y.
Wu, Y. Peng, J. Mol. Catal. A 2006, 259, 7; c) J.-C. Shi, X.
Cao, Y. Zheng, L. Jia, Chin. J. Org. Chem. 2007, 27, in press.
[6] a) T. Weskamp, F. J. Kohl, W. Heiringer, D. Gleich, W. A.
Herrmann, Angew. Chem. Int. Ed. 1999, 38, 2416; b) S. Blech-
ert, H. Wakamatsu, Angew. Chem. Int. Ed. 2002, 41, 794; c)
T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18.
[7] I. E. Marko, S. Sterin, O. Buisine, G. Mignani, P. Branlard, B.
Tinant, J.-P. Declercq, Science 2002, 298, 204.
[8] a) W. A. Herrmann, L. J. Goossen, C. Köcher, G. R. J. Artus,
Angew. Chem. Int. Ed. Engl. 1996, 35, 2805; b) D. Enders, H.
Gielen, G. Raabe, J. Runsink, J. H. Teles, Chem. Ber. 1996, 129,
1483; c) M. Scholl, S. Ding, C. W. Lee, R. H. Grubbs, Org.
Lett. 1999, 1, 953; d) J. Pytkowicz, S. Roland, P. Mangeney, G.
Meyer, A. Jutand, J. Organomet. Chem. 2003, 678, 166; e) L. G.
Bonnet, R. E. Douthwaite, B. M. Kariuki, Organometallics
2003, 22, 4187; f) L. G. Bonnet, R. E. Douthwaite, R. Hodg-
son, Organometallics 2003, 22, 4384; g) M. Alcarazo, S. J. Rose-
blade, E. Alonso, R. Fernández, E. Alvarez, F. J. Lahoz, J. M.
Lassaletta, J. Am. Chem. Soc. 2004, 126, 13242.
yl)imidazolinium chloride (4): A mixture of diaminoethane 3 (2.0 g,
3.4 mmol) and NH4Cl (0.3 g, 5.6 mmol) in triethylorthoformate
(40 mL) was stirred at 110 °C for 3 h. Upon cooling of the reaction
mixture to room temperature, ashen solids appeared and were col-
lected by filtration and washed with hexane. The solid was dis-
solved in dichloromethane and purified through a short column to
remove excess NH4Cl. Yield: 2.0 g (92%). M.p. 153–154 °C. [α]2D0
=
1
+127.9 (c = 1.0, ethanol). H NMR (400 MHz, CDCl3): δ = 8.83
(s, 1 H), 7.40–7.15 (m, 10 H), 5.88 (br., 2 H), 5.50 (s, 2 H), 4.57 (s,
2 H), 4.30–4.05 (m, 8 H), 3.90 (br., 2 H), 3.75–3.60 (m, 4 H), 3.10
(s, 6 H), 3.06 (s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
157.29, 136.96, 129.44, 128.45 (2 C), 126.12 (2 C), 102.55, 100.70,
74.51, 69.30, 66.86, 58.66, 58.22, 55.43, 50.09 ppm. IR (KBr): ν =
˜
3440, 3257, 2930, 1642, 1459, 1409, 1262, 1138, 1104, 995, 964,
772, 707 cm–1. MS (ESI): m/z (%) = 599 (100) [M – Cl]+.
NHC-Coordinated Rh complex 5: A mixture of dried imidazolinium
salt 4 (1.35 g, 2.15 mmol), [RhCl(COD)]2 (0.40 g, 0.82 mmol), and
NaOtBu (0.31 g, 3.2 mmol) was stirred in THF (20 mL) at 45 °C
for 48 h. The reaction mixture was filtered through celite, evapo-
rated, and the residue was then purified by silica gel chromatog-
raphy (2% methanol in dichloromethane). Yield: 1.06 g (77%).
1
M.p. 157–159 °C. H NMR (400 MHz, CDCl3): δ = 7.60–7.20 (m,
11 H), 6.60–6.62 (m, 1 H), 5.80 (br., 1 H), 5.71 (s, 1 H), 5.64 (s, 1
H), 5.05–4.90 (m, 2 H), 4.69 (d, J = 3.2 Hz, 1 H), 4.66 (s, 1 H),
4.42 (br., 1 H), 4.35–4.25 (m, 3 H), 4.11 (br., 2 H), 4.05–3.98 (m, 1
H), 3.92–3.81 (m, 2 H), 3.80–3.65 (m, 5 H), 3.64–3.55 (m, 2 H),
3.46 (s, 3 H), 3.39 (br., 1 H), 3.27 (s, 3 H), 2.55–2.42 (m, 2 H),
2.35–2.22 (m, 2 H), 2.10–1.98 (m, 2 H), 1.82–1.67 (m, 4 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 137 ppm. 65, 137.42, 129.00,
128.56, 128.40, 128.04, 126.30, 126.01, 102.31, 101.40, 101.21,
74.70, 73.80, 71.67, 70.22, 69.94, 69.04, 68.90, 62.41, 61.72, 59.38,
58.52, 55.48, 55.09, 49.23, 47.41, 34.18, 31.68, 29.96, 27.96. IR
[9] M. C. Perry, X. Cui, M. T. Powell, D.-R. Hou, J. H. Reibensp-
ies, K. Burgess, J. Am. Chem. Soc. 2003, 125, 113.
[10] A. O. Larsen, W. Leu, C. N. Oberhuber, J. E. Campbell, A. H.
Hoveyda, J. Am. Chem. Soc. 2004, 126, 11130.
[11] E. Bappert, G. Helmchen, Synlett 2004, 1789.
[12] W.-L. Duan, M. Shi, G.-B. Rong, Chem. Commun. 2003, 2916.
[13] Y. Ma, C. Song, C. Ma, Z. Sun, Q. Chai, M. B. Andrus, Angew.
Chem. Int. Ed. 2003, 42, 5871.
(KBr): ν = 3421, 2933, 2875, 1486, 1452, 1378, 1266, 1133, 1112,
˜
1087, 972, 819, 754, 689 cm–1. MS (ESI): m/z (%) = positive 809
(100) [M – Cl–]; negative 879 (100) [M + Cl–]. HRMS: calcd. for
C39H50N2O10Rh [M – Cl]+ 809.2520; found 809.2529.
[14] a) J.-C. Shi, M.-C. Hong, D. Wu, Q. Liu, B. S. Kang, Chem.
Lett. 1995, 685; b) J.-C. Shi, T. Weng, D. Wu, M. C. Hong, Q.
Liu, B. S. Kang, H. Wang, S. Lu, Chin. J. Chem. 1996, 14, 455.
[15] a) J.-C. Shi, H. Chao, W. Fu, S. M. Peng, C.-M. Che, J. Chem.
Soc., Dalton Trans. 2000, 3128; b) J.-C. Shi, C.-H. Yueng, D.
Wu, Q. Liu, B. S. Kang, Organometallics 1999, 18, 3796; c) J.-
C. Shi, X. Huang, D. Wu, Q. Liu, B. S. Kang, Inorg. Chem.
1996, 35, 2742; d) J.-C. Shi, L. Chen, X. Huang, D. Wu, B. S.
Kang, J. Organomet. Chem. 1997, 535, 17; e) J.-C. Shi, D. Wu,
N,NЈ-1,3-Bis(methyl 4,6-O-benzylidene-3-deoxy-α-D-altropyrano-3-
yl)-2-hydroxyimidazolidine (6): The compound was isolated as a
side product in the preparation of 5; its yield is around 5–20%
1
depending on the dryness of imidazolinium salt 4 used. H NMR
(400 MHz, CDCl3): δ = 8.35 (s, 1 H), 7.50–7.30 (m, 10 H), 5.55 (s,
1 H), 5.44 (s, 1 H), 4.65–4.60 (m, 2 H), 4.35–4.25 (m, 2 H), 4.15–
4.10 (m, 2 H), 4.07–4.00 (m, 2 H), 3.95–3.91 (m, 2 H), 3.90–3.77
(m, 4 H), 3.68–3.60 (m, 2 H), 3.51–3.40 (m, 8 H), 3.38–3.10 (m, 3
Eur. J. Inorg. Chem. 2007, 2221–2224
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
2223