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Table 2 Hydrogenation of various amino acids over Rh-MoOx/SiO2
(entry 4), which is an important intermediate for various useful
chemicals such as medicines16 and X-ray contrast agents.17 Therefore,
Rh-MoOx/SiO2 can be applied to various amino acids without loss of
the optical purity and is very useful from the practical viewpoint.
In conclusion, Rh-MoOx/SiO2 acts as an efficient heteroge-
neous catalyst for hydrogenation of amino acids to amino
alcohols in water. The synergy between MoOx and Rh drastically
improved the activity, selectivity and ee of the produced amino
alcohols. This catalyst can be applied to versatile amino acids
to afford the corresponding amino alcohols in high yields
(90–94%) without loss of the optical purity of the amino acids.
Entry Substrate
Product
Conv./% Yield/% ee/%
1
499.9
99.1
92.8
93.7
499.9
499.9
2a
3
499.9
499.9
92.3
92.8
—
—
4b
5c
6c
7c
499.9
499.9
499.9
92.5
90.5
90.6
n.d.d
Notes and references
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2010, 4, 268.
499.9
n.d.d
8c
9c
99.8
90.0
91.1
—
—
´
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499.9
Reaction conditions: Rh-MoOx/SiO2 (Mo/Rh = 1/8) 100 mg (b200 mg
c500 mg), amino acid (4.5 mmol), H2SO4 5 mmol, H2O 20.0 g, H2 8 MPa
323 K (a313 K). The configuration was not determined.
d
much higher than those of Rh/SiO2. TOF was calculated using the
following equation: TOF = L-alaninol (mmol)/total Rh (mmol)/time
(h). Rh-MoOx/SiO2 provided fifty times higher TOF than Rh/SiO2.
These results indicate that MoOx modification of Rh/SiO2 brings
about not only high TOF and high selectivity but also high ee.
The scope of amino acids was examined over Rh-MoOx/SiO2 at a
lower reaction temperature of 323 K (Table 2). 1 reacted to afford 2 with
a high yield of 92.8% and high selectivity and ee (entry 1). Moreover, at
313 K, 2 was obtained with a higher yield of 93.7% (entry 2). Other
a-amino acids (entries 3–7) were also converted to the corresponding
amino alcohols in high yields (90.5–92.8%) and ee. In addition, the
reactions of b-amino acid and g-amino acid provided the b-amino
alcohol and g-amino alcohol in high yields (entries 8 and 9). It should
be noted that Rh-MoOx/SiO2 enables high yield synthesis of serinol
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Scheme 2 Comparison of performance between Rh-MoOx/SiO2 and
Rh/SiO2. Reaction conditions: catalyst (Mo/Rh = 1/8), L-alanine 0.4 g,
H2SO4 5 mmol, H2O 20.0 g, H2 8 MPa, 353 K. TOF = L-alaninol (mmol)/
total Rh (mmol)/time (h).
13 K.-i. Yamada, M. Nakano, M. Maekawa, T. Akindele and K. Tomioka,
Org. Lett., 2008, 10, 3805.
6658 | Chem. Commun., 2014, 50, 6656--6659
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