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Table 2 Ketone reductions using sodium formate in water
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Entrya
Product
Timeb
Conversion
e.e. (R/S)
1
2
3
4
5
6
7
8
14
16
33
34
17
22
35
20
32
26
26
25
25
25
16
3 h
3 h
3 h
3 h
3 h
4 h
6 h
8 h
24 h
1.5 h
5 h
1 h
4 h
100%
100%
100%
100%
98%
100%
98%
96%
100%
100%
100%
100%
100%
100%
100%
b
96% R
96% R
94% R
93% R
97% R
96% R
91% R
51% R
84% S
97% R
97% R
98% R
98% R
98% R
97% R
9
10
11c
12
13c
14d
15c
a
7 days
16 h
Catalyst R,R-11, S/C
= 200, 28 uC. Time taken to reach
c
conversion indicated. S/C = 1,000. =S/C = 10 000.
d
These results highlight the high stability of tethered catalyst 11,
which can continue to turnover a reaction at exceptionally low
loading in the face of virtually zero background reaction. We
believe that this is one of the first examples of a Rh(III) transfer
hydrogenation system in which the catalyst loadings can be
decreased to levels typically associated with the best of pressure
hydrogenation catalysts.
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We thank the EPSRC for generous support of this work
through postdoctoral funding (to DJM) and Doctoral Training
Funds (to DSM). Dr B. Stein of the EPSRC MS service at
Swansea is thanked for HRMS analysis of certain compounds.
The use of the EPSRC Chemical Database Service at Daresbury is
acknowledged.16 We thank Arran Chemicals for donation of
homochiral diamines.
10 D. M. Matharu, D. J. Morris, A. M. Kawamoto, G. J. Clarkson and
M. Wills, Org. Lett., 2005, 7, 5489.
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˚
10.0963(12), b = 13.7861(16), c = 19.923(2) A, T = 180 K , m(Mo-Ka) =
0.077 mm21, U = 2773.1(6) A , Z 4, Dcal = 1.473 g cm23, 27747
3
˚
reflections measured, 6969 unique [Rint = 0.0312]. Final residuals for
327 parameters were R1 [I . 2s(I)] = 0.0294, wR2 [I . 2s(I)] = 0.0712
and R1 = 0.0309, wR2 = 0.0718 for all 6969 data. CCDC 603515. For
crystallographic data in CIF format or other electronic format see DOI:
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3234 | Chem. Commun., 2006, 3232–3234
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