S.-F. Zhu et al. / Tetrahedron 68 (2012) 7685e7690
7689
Hydrogenation of (E)-isomer (Table 2, entry 9): 95%, ½a D20
ꢁ
ꢂ32.6
HRMS (ESI) Calcd for [MþNa, C15H17NONa]þ: 250.1202; Found:
(c 0.5, CHCl3), 97% ee [HPLC, Chiralcel OB column, n-hexane/2-
propanol¼95:5, 0.8 mL/min, 220 nm UV detector, tR¼25.0 min
(major), tR¼38.8 min (minor)].
250.1208.
Hydrogenation of (E)-isomer (Table 2, entry 13): 95% yield, ½a D20
ꢁ
ꢂ58.4 (c 0.5, CHCl3), 93% ee [HPLC, Chiralcel OB column, n-hexane/
2-propanol¼94:6, 0.8 mL/min, 220 nm UV detector, tR¼43.8 min
(major), tR¼71.8 min (minor)].
Hydrogenation of (Z)-isomer (Table 3, entry 6): 95% yield, ½a D20
ꢁ
þ32.2 (c 0.5, CHCl3), 93% ee.
Hydrogenation of (Z)-isomer (Table 3, entry 8): 96% yield, ½a D20
ꢁ
4.3.3.10. N-(1-(4-Bromophenyl)propan-2-yl)acetamide (2j). 1H
þ52.8 (c 0.5, CHCl3), 91% ee.
NMR (400 MHz, CDCl3)
d
7.37 (d, J¼8.4 Hz, 2H, AreH), 7.02 (d,
J¼8.0 Hz, 2H, AreH), 5.76 (d, J¼7.2 Hz, 1H, NH), 4.21e4.13 (m, 1H,
CH), 2.77 (dd, J¼5.9, 13.5 Hz, 1H, CH2), 2.62 (dd, J¼7.2, 13.5 Hz, 1H,
CH2), 1.89 (s, 3H, CH3), 1.06 (d, J¼6.7 Hz, 3H, CH3); 13C NMR
Acknowledgements
We thank the National Natural Science Foundation of China and
the National Basic Research Program of China (2010CB833300,
2011CB808600), and the ‘111’ project (B06005) of the Ministry of
Education of China for financial support.
(100 MHz, CDCl3)
d 169.3, 137.0, 131.3, 131.0, 120.2, 45.9, 41.7, 23.3,
19.7; IR (neat): 3295s, 3091w, 2963w, 2924w, 2852w, 1644s, 1555s,
1488m, 1448m, 1371m, 1295m, 1202m, 1139m, 1071m, 1012m,
973w, 834w, 798m, 745w, 713w, 640w, 605m, 521m, 420w; HRMS
(ESI) calcd for [MþNa, C11H14BrNONa]þ: 278.0151; Found:
278.0149.
Supplementary data
Hydrogenation of (E)-isomer (Table 2, entry 10): 95% yield, ½a D20
ꢁ
The preparation of substrates, b-arylenamides, NMR spectrum
ꢂ36.4 (c 0.5, CHCl3), 90% ee [HPLC, Chiralcel OB column, n-hexane/
2-propanol¼96:4, 0.8 mL/min, 220 nm UV detector, tR¼34.8 min
(major), tR¼46.9 min (minor)].
for new compounds and GC and HPLC charts for hydrogenation
products are provided. Supplementary data related to this article
4.3.3.11. N-(1-(3-Chlorophenyl)propan-2-yl)acetamide (2k). 1H
NMR (400 MHz, CDCl3)
d 7.24e7.17 (m, 3H, AreH), 7.08e7.06 (m,
References and notes
1H, AreH), 5.91 (d, J¼7.6 Hz, 1H, NH), 4.29e4.16 (m, 1H, CH), 2.83
(dd, J¼5.9, 13.5 Hz, 1H, CH2), 2.66 (dd, J¼7.3, 13.5 Hz, 1H, CH2), 1.93
(s, 3H, CH3), 1.10 (d, J¼6.7 Hz, 3H, CH3); 13C NMR (100 MHz, CDCl3)
1. Chiral Amine Synthesis: Methods, Developments and Applications; Nugent, T. C.,
Ed.; Wiley-VCH: Weinheim, 2010.
2. (a) Snyder, S. H.; Tayler, K. M. Science 1970, 168, 1487; (b) Hajos, G. T.; Garattin,
S. J. Pharm. Pharmacol. 1973, 25, 418.
d
169.4, 140.2, 133.9, 129.5, 128.2, 127.4, 126.5, 46.0, 42.0, 23.3,
19.8; IR (neat): 3296s, 3086w, 2966m, 2925m, 2854w, 1647s,
1555s, 1476m, 1448m, 1426m, 1371m, 1297m, 1202m, 1137m,
1082m, 969w, 853w, 779m, 734m, 705m, 683m, 599m, 465w;
HRMS (ESI) calcd for [MþNa, C11H14ClNONa]þ: 234.0656; Found:
234.0655.
3. Barnes, B. Formoterol, a New Generation of Beta-2-agonist; Hogrefe and Huber:
Toronto, 1991.
4. Sano, M.; Ernesto, C.; Thomas, R. G.; Klauber, M. R. N. Engl. J. Med. 1997, 336,
1216.
~
5. Roehrborn, C. G.; Siami, P.; Barkin, J.; Damiao, R.; Major-Walker, K.; Morrill, B.;
Montorsi, F. J. Urol. 2008, 179, 616.
Hydrogenation of (E)-isomer (Table 2, entry 11): 95% yield, ½a D20
ꢁ
6. (a) Yeung, B. K. S.; Zou, B.; Rottmann, M.; Lakshminarayana, S. B.; Ang, S. H.;
Leong, S. Y.; Tan, J.; Wong, J.; Keller-Maerki, S.; Fischli, C.; Goh, A.; Schmitt, E. K.;
Krastel, P.; Francotte, E.; Kuhen, K.; Plouffe, D.; Henson, K.; Wagner, T.; Winz-
eler, E. A.; Petersen, F.; Brun, R.; Dartois, V.; Diagana, T. T.; Keller, T. H. J. Med.
Chem. 2010, 53, 5155; (b) Bringmann, G.; Gulder, T.; Hertlein, B.; Hemberger, Y.;
Meyer, F. J. Am. Chem. Soc. 2010, 132, 1151.
7. For selected reviews of transition-meal-catalyzed asymmetric hydrogenation
reactions, see: (a) Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A.,
Yamamoto, H., Eds.; Springer: Berlin, 1999; (b) Asymmetric Catalysis on In-
dustrial Scale: Challenges, Approaches and Solutions; Blaser, H.-U., Schmidt, E.,
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2003, 103, 3029.
ꢂ42.2 (c 0.5, CHCl3), 97% ee [HPLC, Chiralcel OD-H column, n-
hexane/2-propanol¼97:3, 1.0 mL/min, 220 nm UV detector,
tR¼28.7 min (major), tR¼33.8 min (minor)].
Hydrogenation of (Z)-isomer (Table 3, entry 7): 95% yield, ½a D20
ꢁ
þ39.8 (c 0.5, CHCl3), 91% ee.
4.3.3.12. N-(1-(3-(Trifluoromethyl)phenyl)propan-2-yl)acetamide
(2l). 1H NMR (400 MHz, CDCl3)
d 7.48e7.37 (m, 4H, AreH), 6.12 (d,
8. For recent reviews, see: (a) Xie, J.-H.; Zhu, S.-F.; Zhou, Q.-L. Chem. Rev. 2011, 111,
1713; (b) Gopalaiah, K.; Kagan, H. B. Chem. Rev. 2011, 111, 4599.
J¼7.2 Hz, 1H, NH), 4.29e4.18 (m, 1H, CH), 2.91 (dd, J¼6.2, 13.5 Hz,
1H, CH2), 2.76 (dd, J¼7.2, 13.5 Hz, 1H, CH2), 1.92 (s, 3H, CH3), 1.12 (d,
9. (a) Chen, J.; Zhang, W.-C.; Geng, H.-L.; Li, W.; Hou, G.-H.; Lei, A.-W.;
Zhang, X.-M. Angew. Chem., Int. Ed. 2009, 48, 800 For an earlier attempt with
51% ee, see: (b) Vineyard, B. D.; Knowles, W. S.; Sabacky, M. J.; Bachman, G. L.;
Weinkauff, D. J. J. Am. Chem. Soc. 1977, 99, 5946.
10. Beckmann rearrangement of ketoximes, see: (a) Brettle, R.; Shibib, S. M.;
Wheeler, K. J. J. Chem. Soc., Perkin Trans. 1 1985, 831 reduction of nitroalkene,
see: (b) Laso, N. M.; Quiclet-Sire, B.; Zard, S. Z. Tetrahedron Lett. 1996, 37, 1605
reductive acylation of ketoximes, see: (c) Burk, M. J.; Casy, G.; Johnson, N. B. J.
Org. Chem. 1998, 63, 6084; (d) Zhu, G.-X.; Casalnuovo, A. L.; Zhang, X. M. J. Org.
Chem. 1998, 63, 8100; (e) Tang, W.-J.; Capacci, A.; Sarvestani, M.; Wei, X.-D.; Yee,
N. K.; Senanayake, C.-H. J. Org. Chem. 2009, 74, 9528; (f) Guang, Z.-H.; Zhang, Z.-
Y.; Ren, Z.-H.; Wang, Y.-Y.; Zhang, X.-M. J. Org. Chem. 2011, 76, 339 The
palladium-catalyzed cross coupling between enolates with amides can produce
J¼6.7 Hz, 3H, CH3); 13C NMR (100 MHz, CDCl3)
d 169.5, 139.2, 132.6,
130.5 (q, J¼31.7 Hz), 128.7, 124.1 (q, J¼270.5 Hz), 125.9 (q, J¼3.6 Hz),
123.1 (q, J¼3.6 Hz), 46.1, 42.1, 23.1, 19.7; IR (neat): 3298s, 3093w,
2971w, 2931w, 1646s, 1556m, 1455m, 1374m, 1330s, 1205m, 1161m,
1115s,1076m, 970w, 921w, 867w, 799m, 706m, 664m, 607m, 520m,
426w; HRMS (ESI) calcd for [MþNa, C12H14F3NONa]þ: 268.0920;
Found: 268.0925.
Hydrogenation of (E)-isomer (Table 2, entry 12): 96% yield, ½a D20
ꢁ
ꢂ31.4 (c 0.5, CHCl3), 95% ee [HPLC, Chiralcel OB column, n-hexane/
2-propanol¼96:4, 0.8 mL/min, 220 nm UV detector, tR¼17.7 min
(major), tR¼26.8 min (minor)].
the
b-arylenamides with highly Z/E selectivity; however, it is less atom-
economy comparing to the above methods, see: (g) Wallace, D. J.; Klauber,
D. J.; Chen, C.-Y.; Volante, R. P. Org. Lett. 2003, 5, 4749.
11. For reviews, see: (a) Xie, J.-H.; Zhou, Q.-L. Acc. Chem. Res. 2008, 41, 581; (b) Ding,
K.-L.; Han, Z.-B.; Wang, Z. Chem.dAsian J. 2009, 4, 32 For examples, see: (c) Fu,
Y.; Xie, J.-H.; Hu, A.-G.; Zhou, H.; Wang, L.-X.; Zhou, Q.-L. Chem. Commun. 2002,
480; (d) Hu, A.-G.; Fu, Y.; Xie, J.-H.; Zhou, H.; Wang, L.-X.; Zhou, Q.-L. Angew.
Chem., Int. Ed. 2002, 41, 2348; (e) Zhu, S.-F.; Fu, Y.; Xie, J.-H.; Liu, B.; Xing, L.;
Zhou, Q.-L. Tetrahedron: Asymmetry 2003, 14, 3219; (f) Fu, Y.; Guo, X.-X.; Zhu, S.-
F.; Hu, A.-G.; Xie, J.-H.; Zhou, Q.-L. J. Org. Chem. 2004, 69, 4648; (g) Fu, Y.; Hou,
G.-H.; Xie, J.-H.; Xing, L.; Wang, L.-X.; Zhou, Q.-L. J. Org. Chem. 2004, 69, 8157;
(h) Hou, G.-H.; Xie, J.-H.; Wang, L.-X.; Zhou, Q.-L. J. Am. Chem. Soc. 2006, 128,
11774; (i) Huo, X.-H.; Xie, J.-H.; Wang, Q.-S.; Zhou, Q.-L. Adv. Synth. Catal. 2007,
349, 2477; (j) Hou, G.-H.; Xie, J.-H.; Yan, P.-C.; Zhou, Q.-L. J. Am. Chem. Soc. 2009,
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4.3.3.13. N-(1-(Naphthalen-2-yl)propan-2-yl)acetamide (2m).
1H NMR (400 MHz, CDCl3)
d 7.81e7.76 (m, 3H, AreH), 7.61 (s, 1H,
AreH), 7.47e7.41 (m, 2H, AreH), 7.34e7.31 (m, 1H, AreH), 5.56 (br,
1H, NH), 4.39e4.30 (m, 1H, CH), 3.00 (dd, J¼5.7, 13.5 Hz, 1H, CH2),
2.84 (dd, J¼7.4, 13.5 Hz, 1H, CH2), 1.91 (s, 3H, CH3), 1.13 (d, J¼6.7 Hz,
3H, CH3); 13C NMR (100 MHz, CDCl3)
d 169.3, 135.5, 133.4, 132.1,
127.9, 127.8, 127.7, 127.6, 127.4, 126.0, 125.4, 46.1, 42.5, 23.4, 19.9; IR
(neat): 3282s, 3073w, 2970w, 2929w, 1638s, 1557s, 1446w, 1371m,
1294w, 1160w, 1124w, 974w, 865w, 819m, 749m, 603m, 483m;