Albrecht Berkessel and Erkan Ertürk
FULL PAPERS
to those for the synthesis of the chromium complex 8 (see
above). Employing the ligand 15 (236 mg, 0.50 mmol), CrCl2
14361–14384; b) E. N. Jacobsen, Acc. Chem. Res. 2000,
33, 421–431.
(
68 mg, 0.55 mmol), and triethylamine (101 mg, 1.00 mmol)
in 40 mL of absolute THF, the chromium(III) complex 16
was obtained as a brown solid; yield: 243 mg (0.44 mmol,
[3] A. Gansäuer, T. Lauterbach, S. Narayan, Angew.
Chem. Int. Ed. 2003, 42, 5556–5573.
AHCTREUNG
[4] ARO of meso-epoxides with water: a) J. M. Ready,
E. N. Jacobsen, J. Am. Chem. Soc. 2001, 123, 2687–
2688; with carboxylic acids: b) E. N. Jacobsen, F. Ka-
kiuchi, R. G. Konsler, J. F. Larrow, M. Tokunaga, Tetra-
hedron Lett. 1997, 38, 773–776; with phenols: c) T.
Iida, N. Yamamoto, S. Matsunaga, H.-G. Woo, M. Shi-
basaki, Angew. Chem. Int. Ed. 1998, 37, 2223–2226;
d) S. Matsunaga, J. Das, J. Roels, E. M. Vogl, N. Yama-
moto, T. Iida, K. Yamaguchi, M. Shibasaki, J. Am.
Chem. Soc. 2000, 122, 2252–2260; with arylselenols:
e) M. Yang, C. Zhu, F. Yuan, Y. Huang, Y. Pan, Org.
Lett. 2005, 7, 1927–1930; with thiols: f) H. Yamashita,
Bull. Chem. Soc. Jpn. 1988, 61, 1213–1220; g) T. Iida,
N. Yamamoto, H. Sasai, M. Shibasaki, J. Am. Chem.
Soc. 1997, 119, 4783–4784; h) M. H. Wu, E. N. Jacob-
sen, J. Org. Chem. 1998, 63, 5252–5254; with amines:
i) H. Yamashita, Chem. Lett. 1987, 525–528; j) C.
Schneider, A. R. Sreekanth, E. Mai, Angew. Chem. Int.
Ed. 2004, 43, 5691–5694; k) F. Carrꢂe, R. Gil, J. Collin,
Org. Lett. 2005, 7, 1023–1026; l) S. Azoulay, K.
Manabe, S. Kobayashi, Org. Lett. 2005, 7, 4593–4595;
8
1
(
7%); FT-IR (film): n˜ =2959, 1717, 1606, 1444, 1308, 1259,
-1
175, 1027, 866, 799, 766 cm ; UV-Vis (CH Cl ): l
max
2
2
abs.)=250 (0.88), 402 nm (0.20); HR-ESI-MS (CH Cl /
2 2
52
MeOH): m/z=551.964, calcd. for C H Cl CrN O ([M-
2
2
20
4
2
3
+
A
C
H
T
R
E
U
N
G
(MeOH)ÀCl] ): 551.963; ESI-MS (CH Cl -MeOH): m/z
2
2
(
%)=559 (2), 558 (11), 557 (21), 556 (57), 554 (100, [M-
54 + 53 +
A
C
H
T
R
E
U
N
G
( Cr)ÀCl+MeOH] ), 553 (31, [M
ACHTREUNG
52
ACHTREUNG
+
5
52 (74, [M
5
4
+
52
+
A
C
H
T
R
E
U
N
G
( Cr)ÀCl] ), 520 (11, [M( Cr)ÀCl] ).
A
H
R
U
G
(
1S,2S,4S,5S)-N,N’-Bis-(3,5-dichlorosalicylidene)-2,5-
diaminobicyclo[2.2.1]heptanechromium(III) p-Tolu-
enesulfonate [17]
A
C
H
T
R
E
U
N
G
ACHTREUNG
The anion exchange was conducted under conditions analo-
gous to those for the synthesis of the chromium complex 9
(
(
see above). Employing the chromium
A
H
R
U
G
115 mg, 0.20 mmol) and AgOTs (62 mg, 0.22 mmol) in a
mixture of 15 mL absolute THF and 50 mL acetonitrile gave
the complex 17 as a brown solid; yield: 115 mg (0.17 mmol,
8
1
3%); FT-IR (film): n˜ =2958, 1719, 1605, 1443, 1308, 1259,
173, 1025, 865, 798, 766, 732; UV-Vis (CH Cl ): l
max
with TMSN : m) W. A. Nugent, J. Am. Chem. Soc.
3
2
2
1
992, 114, 2768–2769; n) L. M. Martꢃnez, J. L. Leight-
on, D. H. Carsten, E. N. Jacobsen, J. Am. Chem. Soc.
995, 117, 5897–5898; o) B. W. McCleland, W. A.
Nugent, M. G. Finn, J. Org. Chem. 1998, 63, 6656–
666; with TMSCN: p) B. M. Cole, K. D. Shimizu,
(
abs.)=250 (1.86), 398 nm (0.37); ESI-MS (CH Cl /MeOH):
2 2
m/z (%)=559 (6), 558 (14), 557 (11), 556 (46), 554 (100, [M-
1
5
4
+
53
A
C
H
T
R
E
U
N
G
( Cr)ÀOTs+MeOH] ),
553
(23,
[M
A
T
E
N
( Cr)ÀOTs+
+
52
ACHTREUNG
+
MeOH] ), 552 (81, [M
( Cr)ÀOTs+MeOH] ), 522 (6, [M-
6
54
+
52
+
A
C
H
T
R
E
U
N
G
( Cr)ÀOTs] ), 520 (3, [M( Cr)ÀOTs] ).
A
H
R
U
G
C. A. Krueger, J. P. A. Harrity, M. L. Snapper, A. H.
Hoveyda, Angew. Chem. Int. Ed. 1996, 35, 1668–1671;
q) S. E. Schaus, E. N. Jacobsen, Org. Lett. 2000, 2,
1001–1004; with PhCCLi: r) C. Zhu, M. Yang, J. Sun,
Y. Zhu, Y. Pan, Synlett 2004, 465–468; with PhLi: s) N.
Oguni, Y. Miyagi, K. Itoh, Tetrahedron Lett. 1998, 39,
Representative Procedure for the HKR of Terminal
Epoxides (Table 2)
To the mixture of the racemic epoxide (1.00 eq) and the cat-
alyst 9 (0.05–2.50 mol%) (in a solvent, if necessary) was
added water (0.55 equivs.). Approx. 50 mL samples were
taken periodically, diluted with 200 mL of ethyl acetate, and
filtered through a plug of neutral alumina. The latter was
flushed with ethyl acetate or diethyl ether. The enantiomeric
excesses of the starting epoxide and the product diol were
followed by means of chiral GC. Upon detection of >99%
ee for the epoxide, the reaction was stopped. The epoxide
9
023–9026; t) E. Vrancken, A. Alexakis, P. Mangeney,
Eur. J. Org. Chem. 2005, 1354–1366; with SiCl4:
u) S. E. Denmark, P. A. Barsanti, K.-T. Wong, R. A.
Stavenger, J. Org. Chem. 1998, 63, 2428–2429; v) S.
Reymond, O. Legrand, J. M. Brunel, G. Buono, Eur. J.
Org. Chem. 2001, 2819–2823; with TMSBr: w) W. A.
Nugent, J. Am. Chem. Soc. 1998, 120, 7139–7140; by
electron transfer: x) A. Gansäuer, T. Lauterbach, H.
Bluhm, M. Noltemeyer, Angew. Chem. Int. Ed. 1999,
(
(
10a–h) and the diol (11a–i) were isolated by fractionating
vacuum) distillation (see Supporting Information).
3
8, 2909–2910.
[
5] Reviews on kinetic resolution: a) J. M. Keith, J. F.
Larrow, E. N. Jacobsen, Adv. Synth. Catal. 2001, 343,
5
–26; b) E. Vedejs, M. Jure, Angew. Chem. Int. Ed.
Acknowledgements
2005, 44, 3974–4001.
[
6] a) M. Tokunaga, J. F. Larrow, F. Kakiuchi, E. N. Jacob-
sen, Science 1997, 277, 936–938; b) S. E. Schaus, B. D.
Brandes, J. F. Larrow, M. Tokunaga, K. B. Hansen,
A. E. Gould, M. E. Furrow, E. N. Jacobsen, J. Am.
Chem. Soc. 2002, 124, 1307–1315; c) L. P. C. Nielsen,
C. P. Stevenson, D. G. Blackmond, E. N. Jacobsen, J.
Am. Chem. Soc. 2004, 126, 1360- 1362.
7] For a recent example of enzymatic/microbial synthesis
of chiral a-halohydrins as chiral epoxide precursors,
see: T. M. Poessl, B. Kosjek, U. Ellmer, C. C. Gruber,
K. Edegger, K. Faber, P. Hildebrandt, U. T. Bornsche-
This work was supported by the Fonds der Chemischen In-
dustrie.
References
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