4266
W. Chen et al. / Tetrahedron Letters 47 (2006) 4263–4266
Table 4. Asymmetric hydrogenation of b-dehydroamino acid deriva-
tives
Amore, A.; vanHeerbeek, R.; Back, J. W.; Hiemstra, H.;
Reek, J. N. H.; van Maarseveen, J. H. Tetrahedron Lett.
a
2
004, 45, 5999–6002; (f) Bernsmann, H.; van den Berg, M.;
H , L-Rh(COD) TfO
AcNH
2
2
AcNH
Hoen, R.; Minnaard, A. J.; Mehler, G.; Reetz, M. T.; de
Vries, J. G.; Feringa, B. L. J. Org. Chem. 2005, 70, 943–
951; (g) Reetz, M. T.; Ma, J.-A.; Goddard, R. Angew.
Chem., Int. Ed. 2005, 44, 412–415; (h) Hagemann, B.;
Junge, K.; Enthaler, S.; Michalik, M.; Riermeier, T.;
Monsees, A.; Beller, M. Adv. Synth. Catal. 2005, 347,
*
CO Me
CO Me
2
2
CH CL , rt
2
2
Me
S/C
Me
b
c
L
H
2
(psi)
Time (h)
Conv. (%)
ee (%)
1b
2a
2b
3a
3b
100
100
100
100
100
300
300
300
300
300
15
15
15
15
15
78.2
96.4
84.8
80.0
82.3
85.1 (R)
93.7 (R)
96.5 (R)
95.2 (S)
95.1 (S)
1
978–1986; (i) Hoen, R.; Boogers, J. A. F.; Bernsmann,
H.; Minnaard, A. J.; Meetsma, A.; Tiemersma-Wegman,
T. D.; de Vries, A. H. M.; de Vries, J. G.; Feringa, B. L.
Angew. Chem., Int. Ed. 2005, 44, 4209–4212; (j) Reetz, M.
T.; Li, X. Angew. Chem., Int. Ed. 2005, 44, 2959–2962; (k)
Xu, Y.; Alcock, N. W.; Clarkson, G. J.; Docherty, G.;
Woodward, G.; Wills, M. Org. Lett. 2004, 6, 4105–4107;
a
Reaction conditions: 1 mmol of substrate, 0.01 mmol of [Rh-
COD) ]OTf, 0.022 mmol of ligand, 2 mL of CH Cl room
(
2
2
2
,
temperature.
(
(
l) Reetz, M. T.; Li, X. Tetrahedron 2004, 60, 9709–9714;
m) Liu, Y.; Ding, K. J. Am. Chem. Soc. 2005, 127, 10488–
b
c
Ratio of substrate to catalyst.
Determined by GC using Chrompack Chirasil-Dex CB (25 m ·
.25 mm) column.
1
3
0489; (n) Reetz, M. T.; Li, X. Synthesis 2005, 3183–
185.
0
6
. (a) Doherty, S. D.; Robins, E. G.; Pal, I.; Newman, C. R.;
Hardacre, C.; Rooney, D.; Mooney, D. A. Tetrahedron:
Asymmetry 2003, 14, 1517–1527; (b) Huttenloch, O.;
Laxman, E.; Waldmann, H. Chem. Commun. 2002, 673–
dehydroamino acid derivatives and b-dehydroamino
acid derivatives.
1
3
6
74; (c) Huttenloch, O.; Laxman, E.; Waldmann, H.
References and notes
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. For a recent review, see: Tang, W.; Zhang, X. Chem. Rev.
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2
2
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Ed. Engl. 1968, 7, 942–943; (b) Knowles, W. S.; Sabacky,
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. (a) Reetz, M. T.; Mehler, G. Angew. Chem., Int. Ed. 2000,
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3
39, 3889–3890; (b) van den Berg, M.; Minnaard, A. J.;
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1
1540; (c) Claver, C.; Fernandez, E.; Gillon, A.; Heslop,
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13. Asymmetric hydrogenation—general procedure: In a 10 mL
4
5
. For reviews of monophosphorus ligands, see: (a) Koma-
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1
197–1200; (b) Lagasse, F.; Kagan, H. B. Chem. Pharm.
vial, a solution of [Rh(COD)
and ligand (0.011 mmol) in anhydrous and degassed
CH Cl (2 mL) was stirred for 10 min at room tempera-
ture, then the substrate in the desired amount was added.
The vial was placed in a stainless autoclave. The autoclave
was purged three times with H , and the pressure was set
2
to the desired value, and hydrogenation was performed at
room temperature for the appropriate time. After carefully
2
]OTf (2.3 mg, 0.005 mmol)
Bull. 2000, 48, 315–324; (c) Jerphagnon, T.; Renaud, J.-L.;
Bruneau, C. Tetrahedron: Asymmetry 2004, 14, 2101.
. For some other recent examples, see: (a) Huang, H.;
Zheng, Z.; Luo, H.; Bai, C.; Hu, X.; Chen, H. J. Org.
Chem. 2004, 69, 2355–2361; (b) Fu, Y.; Guo, X.-X.; Zhu,
S.-F.; Hu, A.-G.; Xie, J.-H.; Zhou, Q.-L. J. Org. Chem.
2
2
2
004, 69, 4648–4655; (c) Fu, Y.; Hou, G.-H.; Xie, J.-H.;
Xing, L.; Wang, L.-X.; Zhou, Q.-L. J. Org. Chem. 2004,
9, 8157–8160; (d) Wu, S.; Zhang, W.; Zhang, Z.; Zhang,
X. Org. Lett. 2004, 6, 3565–3668; (e) Botman, P. N. M.;
venting the H
diluted with Et
plug. The resulting solution was used directly for analysis.
2
, the reaction mixture was concentrated,
6
2
O and passed through a short silica gel