COMMUNICATIONS
Keywords: alcohols ´ copper ´ galac-
tose oxidase ´ homogeneous catalysis ´
metalloenzymes
[1] a) J. W. Whittaker in Metal Ions in Biological
Systems, Vol. 30 (Eds:. H. Sigel, A. Sigel),
Marcel Dekker, New York, 1994, pp. 315 ±
360; b) P. F. Knowles, N. Ito in Perspectives
in Bio-inorganic Chemistry, Vol. 2 (Eds.:
R. W. Hay, J. R. Dilworth, K. B. Nolan),
Jai, London, 1994, pp. 207 ± 244.
[2] a) N. Ito, S. E. V. Phillips, C. Stevens, Z. B.
Ogel, M. J. McPherson, J. N. Keen, K. D. S.
Yadav, P. F. Knowles, Nature 1991, 350, 87;
b) N. Ito, S. E. V. Phillips, K. D. S. Yadav,
P. F. Knowles, J. Mol. Biol. 1994, 238, 794.
[3] a) R. M. Wachter, M. P. Montague-Smith,
B. P. Branchaud, J. Am. Chem. Soc. 1997,
119, 7743; b) B. P. Branchaud, M. P. Mon-
tague-Smith, D. J. Kosman, F. R. McLaren,
J. Am. Chem. Soc. 1993, 115, 798; c) M. M.
Whittaker, J. W. Whittaker, Biophys. J. 1993,
64, 762; d) R. M. Wachter, B. P. Branchaud,
J. Am. Chem. Soc. 1996, 118, 2782.
[4] A. Maradufu, G. M. Cree, A. S. Perlin, Can.
J. Chem. 1971, 49, 3429.
[5] a) J. A. Halfen, B. Jazdzewski, S. Mahapatra,
L. M. Berreau, E. C. Wilkinson, L. Que, Jr.,
W. B. Tolman, J. Am. Chem. Soc. 1997, 119,
8217; b) A. Sokolowski, H. Leutbecher, T.
Weyhermüller, R. Schnepf, E. Bothe, E. Bill,
P. Hildebrandt, K. Wieghardt, J. Biol. Inorg.
Chem. 1997, 2, 444; c) D. Zurita, I. Gautier-
Luneau, S. Menage, J.-L. Pierre, E. Saint-
Aman, J. Biol. Inorg. Chem. 1997, 2, 46; d) S.
Itoh, S. Takayama, R. Arakawa, A. Furuta,
M. Komatsu, A. Ishida, S. Takamuku, S.
Fukuzumi, Inorg. Chem. 1997, 36, 1407; d) D.
Zurita, S. Menage, J.-L. Pierre, E. Saint-
Aman, New J. Chem. 1997, 21, 1001; e) J.
Müller, T. Weyhermüller, E. Bill, P. Hilde-
brandt, L. Ould-Moussa, T. Glaser, K. Wieg-
hardt, Angew. Chem. 1998, 110, 637;
Angew. Chem. Int. Ed. 1998, 37, 616.
[6] Y. Wang, T. D. P. Stack, J. Am. Chem. Soc.
1996, 118, 13097.
[7] Y. Wang, J. L. DuBois, B. Hedman, K. O.
Hodgson, T. D. P. Stack, Science, 1998, 279,
537.
[8] Crystal structure determination of 1: blue
crystal (0.65 Â 0.45 Â 0.12 mm3); C34H55Cu-
NO2S, Mr 605.4; monoclinic, space group
P21/n, a 15.659(3), b 13.107(3), c
Scheme 2. Proposed mechanisms for the catalytic oxidation of primary and secondary alcohols with 2
according to Equation (4) (A) and Equation (5) (B).
18.321(4) (),
b 105.55(3)o,
V
mMo
3
3623(1) (3), Z 4, T 293(2) K; 1calcd 1.11 g cm
;
found: C 64.01,H 9.04, N 2.20, S 4.83, Cu 9.74; UV/Vis (THF): lmax [nm]
(e [L mol 1 cm 1]): 400sh (ca. 370), 600sh (300), 700 (370).
0.687 mm 1; semiempirical absorption correction, full-matrix, least-
squares refinement on F 2 with 6917 reflections [I > 2s(I)] and 348
variables, final R values: R(F) 0.068 and wR2 0.135. Crystallo-
graphic data (excluding structure factors) for the structure reported in
this paper have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no. CCDC-101165. 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).
2: A suspension of CuCl, LH2, and NEt3 (same amounts as for 1) in dry(!)
THF was heated to reflux Ar for 30 min. A stream of dry dioxygen was
passed through the clear yellow solution at 20oC for 1 h (the absence of
H2O is important). The solution changed from blue to green and a green
precipitate of 2 slowly formed, which was recrystallized from dry THF.
Yield: 0.12 g, 11%. Elemental analysis calcd for C56H80O4S2Cl2Cu2: C 62.32,
H 7.47, S 5.94, Cl 6.57, Cu 11.77; found: C 61.95, H 7.48, S 5.88, Cl 6.47, Cu
11.75; UV/Vis (THF): lmax, [nm] (e [L mol 1 cm 1]): 400sh, 408 (8.0 Â 103),
424sh, 650(660).
[9] Small amounts of acetone are formed from isopropyl alcohol in THF
in the presence of Cuii ions with air (autoxidation?).
[10] I. E. Marko, P. R. Giles, M. Tsukazaki, S. M. Brown, C. J. Urch,
Science 1996, 274, 2044.
[11] S. D. Pastor, J. D. Spivack, L. P. Steinhuebel, J. Heterocycl. Chem.
1984, 21, 1285.
Received: February 19, 1998 [Z11497IE]
German version: Angew. Chem. 1998, 110, 2340 ± 2343
2220
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1998
1433-7851/98/3716-2220 $ 17.50+.50/0
Angew. Chem. Int. Ed. 1998, 37, No. 16