Wei Li et al.
COMMUNICATIONS
Table 2. Ir-catalyzed asymmetric hydrogenation of N-aryl-
(Eds.: M. Beller, C. Bolm), Wiley-VCH, Weinheim,
2004, p 113; b) H.-U. Blaser, F. Spindler, in: Compre-
hensive Asymmetric Caatalysis, Vol. 1, (Eds.: E. N. Ja-
cobsen, A. Pfaltz, H. Yamamoto), Springer Verlag,
Heidelberg, Berlin, 1999, p 247; c) H.-U. Blaser, C.
Malan, B. Pugin, F. Spindler, H. Steiner, M. Studer,
Adv. Synth. Catal. 2003, 345, 1031; d) W. Tang, X.
Zhang, Chem. Rev. 2003, 103, 3029; e) S. Kobayashi, H.
Ishitani, Chem. Rev. 1999, 99, 1069.
ACHTUNGTRENNUNG
imines.[a]
[2] O. R. Thiel, C. Bernard, W. Tormos, A. Brewin, S. Hir-
otani, K. Murakami, K. Saito, R. D. Larsen, M. J. Mar-
tinelli, P. J. Reider, Tetrahedron Lett. 2008, 49, 13.
[3] A. Kessler, H. Faure, C. Petrel, D. Rognan, M. Cꢂsario,
M. Ruat, P. Dauban, R. H. Dodd, J. Med. Chem. 2006,
49, 5119.
[4] S. Hoffmann, M. Nicoletti, B. List, J. Am. Chem. Soc.
2006, 128, 13074.
[5] R. I. Storer, D. E. Carrera, Y. Ni, D. W. C. MacMillan,
J. Am. Chem. Soc. 2006, 128, 84.
[6] C. Li, B. Villa-Marcos, J. Xiao, J. Am. Chem. Soc. 2009,
131, 6967.
[7] a) R. Kadyrov, T. H. Riermeier, Angew. Chem. 2003,
115, 5630; Angew. Chem. Int. Ed. 2003, 42, 5472; b) R.
Kadyrov, T. H. Riermeier, U. Dingerdissen, V. Tararov,
A. Bçrner, J. Org. Chem. 2003, 68, 4067.
[8] a) T. Ohkuma, M. Kitamura, R. Noyori, in: Catalytic
Asymmetric Synthesis, 2nd edn., (Ed.: I. Ojima), Wiley,
New York, 2000, p 1; b) R. Noyori, T. Ohkuma, Angew.
Chem. 2001, 113, 40; Angew. Chem. Int. Ed. 2001, 40,
40.
[a]
[b]
Reaction conditions: 0.1 mmol of substrate in 2 mL of
CH2Cl2, 0.1 mol% of Ir catalyst, room temperature, 12 h,
5 atm H2 pressure.
The enantiomeric excesses were determined by chiral
HPLC or GC.
Agilent 7890 GC equipment and chiral HPLC on Agilent
1200 Series equipment.
[9] a) C. A. Willoughby, S. L. Buchwald, J. Am. Chem. Soc.
1994, 116, 8952; b) J. Bakos, A. Orosz, B. Heil, M.
Laghmari, P. Lhoste, D. Sinou, J. Chem. Soc. Chem.
Commun. 1991, 1684; c) M. J. Burk, J. E. Feaster, J.
Am. Chem. Soc. 1992, 114, 6266; d) F. Spinder, H.-U.
Blaser, Adv. Synth. Catal. 2001, 343, 68; e) C. J. Cobley,
J. P. Henschke, Adv. Synth. Catal. 2003, 345, 195; f) C.
Moessner, C. Bolm, Angew. Chem. 2005, 117, 7736;
Angew. Chem. Int. Ed. 2005, 44, 7564; g) D. Xiao, X.
Zhang, Angew. Chem. 2001, 113, 3533; Angew. Chem.
Int. Ed. 2001, 40, 3425; h) T. Imamoto, N. Iwadate, K.
Yoshida, Org. Lett. 2006, 8, 2289; i) S.-F. Zhu, J.-B. Xie,
Y.-Z. Zhang, S. Li, Q.-L. Zhou, J. Am. Chem. Soc.
2006, 128, 12886; j) M. N. Cheemala, P. Knochel, Org.
Lett. 2007, 9, 3089; k) C. Li, C. Wang, B. Villa-Marcos,
J. Xiao, J. Am. Chem. Soc. 2008, 130, 14450; l) H.
Guan, M. Limura, M. P. Magee, J. R. Norton, G. Zhu,
J. Am. Chem. Soc. 2005, 127, 7805; m) Z. Han, Z.
Wang, X. Zhang, K. Ding, Angew. Chem. 2009, 121,
5449; Angew. Chem. Int. Ed. 2009, 48, 5345.
General Procedure for Asymmetric Hydrogenation
In the nitrogen-filled glovebox, the solid complex {Ir-
ACHTUNGTRENNUNG[(Sp,Rc)-DuanPhos]ACHTUNGTRENNUNG(cod)}BARF (3.1 mg, 0.002 mmol) was
dissolved in degassed CH2Cl2 (10 mL) and equally divided
into 20 vials. To each vial, imine substrate (0.1 mmol, S/C=
1000) was then added to the catalyst solution and 1.5 mL de-
gassed CH2Cl2 were added to each of the vials. The resulting
solution was transferred to an autoclave, which was charged
with 5 atm of H2. The hydrogenation was performed at
room temperature for 12 h and the hydrogen was released
carefully. The solvent was then evaporated and the residue
was purified by column chromatography to give the corre-
sponding hydrogenation product, which was then analyzed
directly by chiral GC (Gamma Dex 225 or Beta Dex 390) or
HPLC (Chiralcel OD-H) to determine the enantiomeric
excess.
ˇ ´
[10] N. Mrsic, A. J. Minnaard, B. L. Feringa, J. G. de Vries,
Acknowledgements
J. Am. Chem. Soc. 2009, 131, 8358. This article was
published during the course of the preparation of this
manuscript.
We gratefully thank the National Institutes of Health
(GM58832) and Merck & Co., Inc. for the financial support.
[11] a) H.-U. Blaser, Adv. Synth. Catal. 2002, 344, 17; b) S. P.
Smidt, A. Pfaltz, Organometallics 2003, 22, 1000; c) Y.
Xu, M. A. Celik, A. L. Thompson, H. Cai, M. Yurtsev-
er, B. Odell, J. C. Green, D. M. P. Mingos, J. M. Brown,
Angew. Chem. 2009, 121, 590; Angew. Chem. Int. Ed.
2009, 48, 582.
References
[1] For reviews, see: a) F. Spindler, H.-U. Blaser, in: Tran-
sition Metals for Organic Synthesis, 2nd edn., Vol. 2,
3126
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2009, 351, 3123 – 3127