Enantioselective Synthesis of Chiral Tetrahydroisoquinolines
FULL PAPERS
[9] <For an early example, see: B. Bartels, G. Helmchen,
Chem. Commun. 1999, 741.
Experimental Section
[10] a) J. W. Faller, S. C. Milheiro, J. Parr, J. Organomet.
General Procedure for the Asymmetric
Hydrogenation of Enamines
ˇ ´
Chem. 2006, 691, 4945; b) N. Mrsic, A. J. Minnaard,
B. L. Feringa, J. G. de Vries, J. Am. Chem. Soc. 2009,
131, 8358.
To a dry Schlenk tube equipped with a stirring bar was
added [IrACHTUNGTRENNUNG(COD)Cl]2 (1.7 mg, 2.5 mmol), (Sa,R,R)-3a (5.6 mg,
[11] a) F. Giacomina, A. Meetsma, L. Panella, L. Lefort,
A. H. M. de Vries, J. G. de Vries, Angew. Chem. 2007,
119, 1519; Angew. Chem. Int. Ed. 2007, 46, 1497; b) G.
Erre, K. Junge, S. Enthaler, D. Addis, D. Michalik, A.
Spannenberg, M. Beller, Chem. Asian J. 2008, 3, 887;
c) S. Enthaler, G. Erre, K. Junge, K. Schrçder, D.
Addis, D. Michalik, M. Hapke, D. Redkin, M. Beller,
Eur. J. Org. Chem. 2008, 3352.
11 mmol) and anhydrous THF (5.0 mL) under a nitrogen at-
mosphere. The mixture was stirred at room temperature for
30 min, and iodine (6.4 mg, 25 mmol) and enamines 1
(0.5 mmol) were added. The nitrogen atmosphere in the
tube was replaced by hydrogen three times and the reaction
solution was stirred at 08C under 1.0 atm H2 for 6–10 h (the
conversion was determined by TLC or GC analysis). After
removed the solvent under vacuum the residue was purified
by flash chromatography on a silica gel column with petrole-
um ether/ethyl acetate. The enantiomeric excess of the prod-
uct was determined by GC, or HPLC, or SFC analysis with
chiral column (see Supporting Information).
ˇ ´
[12] N. Mrsic, L. Lefort, J. A. F. Boogers, A. J. Minnaard,
B. L. Feringa, J. G. de Vries, Adv. Synth. Catal. 2008,
350, 1081.
[13] G. Erre, S. Enthaler, K. Junge, D. Addis, M. Beller,
Adv. Synth. Catal. 2009, 351, 1437.
[14] G.-H. Hou, J.-H. Xie, P.-C. Yan, Q.-L. Zhou, J. Am.
Chem. Soc. 2009, 131, 1366.
[15] For review, see: J. Halpern, in: Asymmetric Synthesis;
(Ed.; J. D. Morrison), Academic Press, Orlando, FL,
1985.
[16] N. E. Lee, S. L. Buchwald, J. Am. Chem. Soc. 1994, 116,
5985.
Acknowledgements
We thank the National Nature Science Foundation of China,
the Major Basic Research Development Program (Grant No.
2006CB806106), the “111” project (B06005) of the Ministry
of Education of China for financial support.
[17] V. I. Tararov, R. Kadyrov, T. H. Riermeier, J. Holz, A.
Bçrner, Tetrahedron Lett. 2000, 41, 2351.
[18] G.-H. Hou, J.-H. Xie, L.-X. Wang, Q.-L. Zhou, J. Am.
Chem. Soc. 2006, 128, 11774.
References
[19] a) P. Cheruku, T. L. Church, A. Trifonova, T. Wart-
mann, P. G. Andersson, Tetrahedron Lett. 2008, 49,
7290; b) A. Baeza, A. Pfaltz, Chem. Eur. J. 2009, 15,
2266.
[1] a) E. N. Jacobsen, A. Pfaltz, H. Yamamoto (Eds), Com-
prehensive Asymmetric Catalysis, 1 st edn., Springer
Verlag, Heidelberg, Berlin, 1999; b) I. Ojima, ACTHNUGTRNEUNG(Ed. ),
[20] For asymmetric hydrogenations of N-unprotected b-
amino-a,b-unsaturated esters or ketones, see: a) X.-B.
Wang, D.-W. Wang, S.-M. Lu, C.-B. Yu, Y.-G. Zhou,
Tetrahedron: Asymmetry 2009, 20, 1040; b) M. Kubryk,
K. B. Hansen, Tetrahedron: Asymmetry 2006, 17, 205;
c) Q. Dai, W. Yang, X. Zhang, Org. Lett. 2005, 7, 5343;
d) Y. Hsiao, N. R. Rivera, T. Rosner, S. W. Krska, E.
Njolito, F. Wang, Y. Sun, J. D. Armstrong, E. J. J. Gra-
bowski, R. D. Tillyer, F. Spindler, C. Malan, J. Am.
Chem. Soc. 2004, 126, 9918.
in: Catalytic Asymmetric Synthesis, 2nd edn., VCH,
New York, 2000; c) G.-Q. Lin, Y.-M. Li, A. S. C. Chan,
Principles and Applications of Asymmetric Synthesis,
Wiley, New York, 2001; d) W. Tang, X. Zhang, Chem.
Rev. 2003, 103, 3029.
[2] a) X. Zhang, T. Taketomi, T. Yoshizumi, H. Kumobaya-
shi, S. Akutagawa, K. Mashima, H. Takaya, J. Am.
Chem. Soc. 1993, 115, 3318; b) T. Shibata, K. Takagi, J.
Am. Chem. Soc. 2000, 122, 9852; c) I. S. Kim, M.-Y.
Ngai, M. J. Krishe, J. Am. Chem. Soc. 2008, 130, 6340.
[3] H.-U. Blaser, Adv. Synth. Catal. 2002, 344, 17.
[4] a) D. Xiao, X. Zhang, Angew. Chem. 2001, 113, 3533;
Angew. Chem. Int. Ed. 2001, 40, 3425; b) Y. Chi, Y.-G.
Zhou, X. Zhang, J. Org. Chem. 2003, 68, 4120.
[5] a) D.-W. Wang, X.-B. Wang, D.-S. Wang, S.-M. Lu, Y.-
G. Zhou, Y.-X. Li, J. Org. Chem. 2009, 74, 2780; b) W.-
B. Wang, S.-M. Lu, P.-Y. Yang, X.-W. Han, Y.-G. Zhou,
J. Am. Chem. Soc. 2003, 125, 10536; c) K. Makino, M.
Iwasaki, Y. Hamada, Org. Lett. 2006, 8, 4573.
[21] J. D. Phillipson, M. F. Roberts, M. H. Zenk, The
Chemistry and Biology of Isoquinoline Alkaloids;
Springer-Verlag, New York, 1985.
[22] K. Achiwa, Heterocycles 1977, 8, 247.
[23] a) R. Noyori, M. Ohta, Y. Hsiao, M. Kitamura, T.
Ohta, H. Takaya, J. Am. Chem. Soc. 1986, 108, 7117;
b) M. Kitamura, Y. Hsiao, R. Noyori, H. Takaya, Tetra-
hedron Lett. 1987, 28, 4829; c) M. Kitamura, Y. Hsiao,
M. Ohta, M. Tsukamoto, T. Ohta, H. Takaya, R.
Noyori, J. Org. Chem. 1994, 59, 297.
[6] M. Eggenstein, A. Thomas, J. Theuerkauf, G. Franci,
[24] Carnegine, see: a) A. B. J. Bracca, T. S. Kaufman, Tetra-
hedron 2004, 60, 10575; armepavine, see: b) A. Zhang,
J. L. Neumeyer, R. J. Baldessarini, Chem. Rev. 2007,
107, 274; glaucine, see: c) E. Anakabe, L. Carrillo, D.
Badꢃa, J. L. Vicario, M. Villegas, Synthesis 2004, 7,
1093; cularine, see: d) R. H. F. Manske, J. Am. Chem.
Soc. 1950, 72, 55.
W. Leitner, Adv. Synth. Catal. 2009, 351, 725.
[7] S. J. Roseblade, A. Pfaltz, Acc. Chem. Res. 2007, 40,
1402.
[8] a) A. J. Minnaard, B. L. Feringa, L. Lefort, J. G. de
Vries, Acc. Chem. Res. 2007, 40, 1267; b) T. Jerphag-
non, J.-L. Renaud, C. Bruneau, Tetrahedron: Asymme-
try 2004, 15, 2101.
Adv. Synth. Catal. 2009, 351, 3243 – 3250
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3249