Chemistry Letters Vol.33, No.3 (2004)
295
Table 1. Palladium-catalyzed deuteration of organic com-
pounds under hydrothermal conditiona
The mechanistic studies have not been examined yet. How-
ever, the method can be applied to various types of compounds
to obtain the fully deuterated compounds which have a potential
for optical communication.16
Run Substrate
Time /h D /%b Yield /%c
1
2
3
4
5
6
7
8
9
Cyclooctene
4
6
4
16
10
12
4
10
11
>95
>95
>95
76
>95
>95
>95
>95
>95
80
84
99
98
86
83
87
99
93
Cyclododecane
Cyclopentadecane
n-Pentadecane
We thank Dr. Yuki Yamasaki (Osaka Prefectural College of
Technology) for offering us autoclave. This work was supported
financially by Kyoto University, International Innovation Cen-
tre. The financial support by Chugai Pharmaceutical Co., Ltd.
and Takahashi Industrial and Economical research foundation
are also acknowledged.
Cyclooctanone
Cyclodecanone
Cyclododecanone
Cyclopentadecanone
2-Dodecanone
References and Notes
1
aSubstrate (5.0 mmol), Pd/C (10 wt % palladium on carbon,
D. C. Rideout and R. Breslow, J. Am. Chem. Soc., 102, 7816
(1980).
100mg, 2 mol % Pd), and D2O (20.0 g). bThe ratios were
1
2
determined by GC, H NMR, H NMR, and mass spectra.
cThe yields were isolated yields.
2
3
Y. M. Lindstrom, Chem. Rev., 102, 2751 (2002).
¨
D. Broll, C. Kaul, A. Kramer. P. Krammer, T. Richter, M.
¨
¨
Jung, H. Vogel, and P. Zehner, Angew. Chem., Int. Ed. Engl.,
38, 2998 (1999).
N. Akiya and P. E. Savage, Chem. Rev., 102, 2725 (2002);
P. E. Savage, Chem. Rev., 99, 603 (1999).
A. R. Katritzky, S. M. Allin, and M. Siskin, Acc. Chem. Res.,
29, 399 (1996).
P. E. M. Siegbahn, M. R. A. Blomberg, and M. Svensson, J.
Phys. Chem., 97, 2564 (1993).
P. Reardon, S. Metts, C. Crittendon, P. Daugherity, and E. J.
Parsons, Organometallics, 14, 3810 (1995); L. U. Gron, J. E.
LaCroix, C. J. Higgins, K. L. Steelman, and A. S. Tinsley,
Tetrahedron Lett., 42, 8555 (2001).
J. R. Jones, W. J. S. Lockley, S.-Y. Lu, and S. P. Thompson,
Tetrahedron Lett., 42, 331 (2001).
Y. Yamasaki, H. Enomoto, N. Yamasaki, and M. Nakahara,
Bull. Chem. Soc. Jpn., 73, 2687 (2000). The vessel in Figure 1
is designed to release the internal overpressure. It is commer-
cially available from Shikokurika Co., Ltd., Kochi, Japan.
octenes would give cyclohexene derivatives. The base catalyzed
H–D exchange reactions are applicable for aromatic compounds
and ketones. The metal catalyzed H–D exchange reaction using
D2 is classical and general method for hydrocarbons, but also
contains a limitation of the substrates because it is gas phase re-
action. Our method is so simple procedure that is applicable to
examine the wide range of compounds. It should be noted that
partial H–D exchange reaction were also performed under mi-
crowave irradiation14 and under an effect of transition metal cat-
alyst in D2O.15
The C–H bonds in benzene ring were also converted into C–
D bonds under the conditions. As shown in Scheme 3, t-butyl
benzene (4) was treated with the same condition in Table 1, a re-
gioselective deuteration was observed in benzene ring. At the
sterically hindered ortho positions, the exchange reaction was
not observed. At the tertiary butyl group, 45% of C–H bonds
were transformed into C–D bonds. In Scheme 4, biphenyl (6)
was converted into the fully deuterated biphenyl (7) completely.
4
5
6
7
8
9
10 Cyclododecane was not detected.
11 N. H. Werstiuk and T. Kadai, Can. J. Chem., 63, 530 (1985);
N. H. Werstiuk and T. Kadai, Can. J. Chem., 52, 2169
(1974).
12 J. Yao and R. F. Evilia, J. Am. Chem. Soc., 116, 11229
(1994); T. Junk and W. J. Catallo, Tetrahedron Lett., 37,
3445 (1996).
D
H
10 wt% Pd/C ( 2 mol%)
t-Bu
D
t-Bu
D2O, 250 °C, 10 h
H
D
4
45%D
80%
5
13 J. G. Atkinson, M. O. Luke, and R. S. Stuart, Can. J. Chem.,
45, 1511 (1967).
Scheme 3.
14 J. R. Jones, W. J. S. Lockley, S.-Y. Lu, and S. P. Thompson,
Tetrahedron Lett., 42, 331 (2001); K. Fodor-Csorba, G.
D
´
Galli, S. Holly, and E. Gacs-Baitz, Tetrahedron Lett., 43,
D
D
3789 (2002); J. M. Barthez, A. V. Filikov, L. B. Frederiksen,
M.-L. Huguet, J. R. Jones, and S.-Y. Lu, Can. J. Chem., 76,
726 (1998).
10 wt% Pd/C ( 2 mol%)
D
D
D
D2O, 250 °C, 14 h
D
15 F. A. L Anet and M. St. Jacques, J. Am. Chem. Soc., 88, 2585
(1966); J. L. Ganett and R. J. Hodges, J. Am. Chem. Soc., 89,
4545 (1967); O. Desponds and M. Schlosser, Tetrahedron
Lett., 37, 47 (1996).
16 T. Kaino, K. Jinguji, and S. Nara, Appl. Phys. Lett., 42, 567
(1983).
D
D
D
6
7
88%
Scheme 4.
Published on the web (Advance View) February 9, 2004; DOI 10.1246/cl.2004.294