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3H), 6.97 (s, 4H), 6.44 (d, J 2.6 Hz, 2H), 2.34 (s, 12H), 2.21 (s, 6H); MS
Enantioselective Ring Opening of Epoxides
with 4-Methoxyphenol Catalyzed by Gallium
Heterobimetallic Complexes: An Efficient
Method for the Synthesis of Optically Active
1,2-Diol Monoethers**
(EI): m/z: 448 [MH] ; elemental analysis calcd for C29H29N5: C 77.8, H
6.53, N 15.6; found: C 77.3, H 6.65, N 15.4.
[Cu(LH)2](BF4)2: MS (FAB): m/z: 485 [63Cu(LH)2] , 274 [63Cu(LH)] ;
elemental analysis calcd for C22H18B2CuF8N10: C 40.1, H 2.75, N 21.2;
found: C 39.6, H 2.74, N 20.8; UV/Vis (MeCN): nÄmax [103 cm 1] (emax
[m 1 cm 1]) 14.3 (58), 24.4 (105), 32.8 (27700), 36.7 (35100),
37.7(31900), 40.2 (44700).
Takehiko Iida, Noriyoshi Yamamoto,
Shigeki Matsunaga, Hee-Gweon Woo, and
Masakatsu Shibasaki*
[Cu(LMes)2](BF4)2: MS (FAB): m/z: 958 [63Cu(LMes)2] , 510 [63Cu(LMes)] ;
elemental analysis calcd for C58H58B2CuF8N10: C 61.5, H 5.16, N 12.4;
found: C 61.3, H 5.17, N 12.3; UV/Vis (MeCN): nÄmax [103 cm 1] (emax
[m 1 cm 1]) 14.4 (46), 24.0 (sh), 29.8 (25200), 30.6 (sh), 35.5 (sh), 36.6
(31100), 45.4 (sh).
The enantioselective ring opening of achiral epoxides by
nucleophilic addition is an attractive method, which is
invaluable in asymmetric synthesis.[1] We reported recently
an asymmetric ring opening reaction of epoxides with tBuSH
that is catalyzed by a Ga-Li-bis(binaphthoxide) complex
(GaLB) in the presence of 4- molecular sieves (Scheme 1).[2]
The high enantioselectivity of these reactions prompted us to
[Cu(LMes)2](ClO4)2: elemental analysis calcd for C58H58Cl2CuN10O8: C 60.2,
H 5.05, N 12.1; found: C 59.4, H 5.03, N 11.9.
Crystal data for [Cu(LH)2](BF4)2: C22H18B2CuF8N10, crystal dimensions
0.50 Â 0.50 Â 0.30 mm, monoclinic, space group P21 (no. 4), a 8.4555(13),
b 8.531(2), c 18.828(5) , b 96.639(13)8; V 1349.0(5) 3, 1calcd
1.624 gcm 3; Siemens P4 diffractometer, 4 ꢀ 2q ꢀ 508, MoKa radiation,
l 0.71073 , q/2q scans, T 223(2) K; of 3515 measured reflections, 2893
were independent and 2000 were observed with I > 2s(I), 10 ꢀ h ꢀ 1,
1 ꢀ k ꢀ 10, 22 ꢀ l ꢀ 22; R 0.048, wR 0.129, GOF 0.972 for 388
parameters, Flack parameter 0.02(3), D1max 0.59 e 3. Crystal data
for [Cu(LMes)2](ClO4)2 ´ 2CH3NO2: C60H64Cl2CuN12O12, crystal dimensions
0.30 Â 0.25 Â 0.25 mm, monoclinic, space group P21/c (no. 14), a
12.048(4), b 19.808(8), c 25.36(2) , b 99.92(4)8; V 5963(5) 3,
1calcd 1.426 gcm 3; Rigaku AFC7R diffractometer, 5 ꢀ 2q ꢀ 508, MoKa
radiation, l 0.71069 , w/2q scans, T 180(2) K; of 12975 measured
reflections, 10518 were independent and 6041 were observed with I >
2s(I), 0 ꢀ h ꢀ 14, 0 ꢀ k ꢀ 23, 30 ꢀ l ꢀ 29; R 0.083, wR 0.309, GOF
1.040 for 784 parameters, D1max 1.10e 3. The structures were solved by
R
R
O
O
O
O
Ga
M
R
R
(R)-GaLB*: R =
(R)-GaHB
SiEt3, M = Li
(R)-GaLB: R = H, M = Li
(R)-GaSB
: R = H, M = H
: R = H, M = Na
Scheme 1. Proposed structures of Ga-M-bis(binaphthoxide) (GaMB) and
of Ga-Li-bis((6,6'-(triethylsilyl)-ethynyl)binaphthoxide) (GaLB*).
direct methods (SHELXTL Plus[12]
) and developed by least-squares
refinement against j F 2 j (SHELXL93[13]). All non-hydrogen atoms were
refined anisotropically, and hydrogen atoms were placed in calculated
positions. Crystallographic data (excluding structure factors) for the
structures reported in this paper have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication no. CCDC-
101277. Copies of the data can be obtained free of charge on application to
CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: (44)1223-336-
033; e-mail: deposit@ccdc.cam.ac.uk).
investigate the possible use of other nucleophiles. Oxygen
nucleophiles are interesting candidates since their reaction
with achiral epoxides provides an effective route to valuable
chiral building blocks such as 1,2-diol derivatives.[3] Quite
recently Jacobsen et al. reported the enantioselective ring
opening of symmetrical epoxides with carboxylic acids, and an
efficient kinetic resolution of racemic terminal epoxides with
water by using a (salen)Coii catalyst (salen N,N'-bis(salicyl-
idene)ethylenediamine dianion).[4] However, this type of
reaction has not been realized so far with alcohols or phenols.
Herein we report the development of a catalytic enantiose-
lective ring opening of epoxides with 4-methoxyphenol by
utilizing gallium heterobimetallic complexes.
Received: March 27, 1998 [Z11650IE]
German version: Angew. Chem. 1998, 110, 2344 ± 2346
Keywords: copper ´ EPR spectroscopy ´ Jahn ± Teller dis-
tortion ´ N ligands
[1] B. J. Hathaway in Comprehensive Coordination Chemistry, Vol. 5
(Eds.: G. Wilkinson, R. D. Gillard, J. E. McCleverty), Pergamon,
Oxford, 1987, pp. 610 ± 611.
[2] Recent reviews: a) C. J. Simmons, New J. Chem. 1993, 17, 77 ± 95;
b) M. A. Hitchman, Comments Inorg. Chem. 1994, 15, 197 ± 254;
c) L. R. Falvello, J. Chem. Soc. Dalton Trans. 1997, 4463 ± 4475.
[3] R. Allmann, W. Henke, D. Reinen, Inorg. Chem. 1978, 27, 378 ± 382.
Hydroxyarene derivatives, such as 4-chlorophenol, 2,4-
dinitrophenol, and 4-methoxyphenol, were first examined as
nucleophiles for the epoxide opening reaction [Eq. (1)]
[*] Prof. Dr. M. Shibasaki, Dr. T. Iida, N. Yamamoto, S. Matsunaga
Graduate School of Pharmaceutical Sciences
The University of Tokyo
Â
[4] M. I. Arriortua, T. Rojo, J. M. Amigo, G. Germain, J. P. Declercq, Acta
Hongo, Bunkyo-ku, Tokyo 113-0033 (Japan)
Fax: (81)3-5684-5206
Crystallogr. Sect. B 1982, 38, 1323 ± 1324.
Â
[5] J.-V. Folgado, W. Henke, R. Allmann, H. Stratemeier, D. Beltran-
Porter, T. Rojo, D. Reinen, Inorg. Chem. 1990, 29, 2035 ± 2042.
[6] W. Henke, D. Reinen, Z. Anorg. Allg. Chem. 1977, 436, 187 ± 200.
[7] D. L. Jameson, K. A. Goldsby, J. Org. Chem. 1990, 55, 4992 ± 4994.
[8] D. L. Jameson, J. K. Blaho, K. T. Kruger, K. A. Goldsby, Inorg. Chem.
1989, 28, 4312 ± 4314.
[9] A. L. Rheingold, C. B. White, S. Trofimenko, Inorg. Chem. 1993, 32,
3471 ± 3477.
[10] A. B. P. Lever, Inorganic Electronic Spectroscopy, 2nd ed., Elsevier,
Amsterdam, 1984, pp. 554 ± 572.
Prof. Dr. H.-G. Woo
Department of Chemistry, College of Natural Science
Chonnam National University
300 Yongbong-Dong, Puk-Ku, Kwangju 500 ± 757 (Republic of
Korea)
Fax: (82)62-530-3389;
[**] We are grateful to Prof. H. Sasai for his generous support. This study
was financially supported by CREST, the Japan Science and
Technology Corporation (JST), and by a Grant-in Aid for Scientific
Research from the Japanese Ministry of Education, Science, and
Culture.
[11] B. A. Goodman, J. B. Raynor, Adv. Inorg. Chem. 1970, 13, 135 ± 362.
[12] G. M. Sheldrick, SHELXTL Plus, PC version, Siemens Analytical
Instruments Inc., Madison, WI, 1990.
[13] G. M. Sheldrick, SHELXL 93, Universität Göttingen, 1993.
Angew. Chem. Int. Ed. 1998, 37, No. 16
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