LETTER
Chiral Acylation Catalysts: A Complete Selectivity Switch
1733
Table 3 Selected 1H NMR Data for 1a, 8, 21 and Methylated/Acyl-
ated Analogues
(3) For examples, see: (a) Vedejs, E.; Daugulis, O.; Diver, S. T.
J. Org. Chem. 1996, 61, 430. (b) Vedejs, E.; Daugulis, O. J.
Am. Chem. Soc. 1999, 121, 5813. (c) Vedejs, E.; Daugulis,
O. J. Am. Chem. Soc. 2003, 125, 4166. (d) MacKay, J. A.;
Vedejs, E. J. Org. Chem. 2004, 69, 6934.
N
O
N
N
O
N
N
O
(4) Mizuta, S.; Sadamori, M.; Fujimoto, T.; Yamamoto, I.
Angew. Chem. Int. Ed. 2003, 42, 3383.
5
6
5
6
5
6
N
N
N
(5) For representative examples, see: (a) Vedejs, E.; Chen, X. J.
Am. Chem. Soc. 1996, 118, 1809. (b) Kawabata, T.; Nagato,
M.; Takasu, K.; Fuji, K. J. Am. Chem. Soc. 1997, 119, 3169.
(c) Ruble, J. C.; Tweddell, J.; Fu, G. C. J. Org. Chem. 1998,
63, 2794. (d) Spivey, A. C.; Fekner, T.; Adams, H.
Tetrahedron Lett. 1998, 39, 8919. (e) Tao, B.; Ruble, J. C.;
Hoic, D. A.; Fu, G. C. J. Am. Chem. Soc. 1999, 121, 5091.
(f) Tao, B.; Ruble, J. C.; Hoic, D. A.; Fu, G. C. J. Am. Chem.
Soc. 1999, 121, 10452. (g) Spivey, A. C.; Fekner, T.; Spey,
S. E.; Adams, H. J. Org. Chem. 1999, 64, 9430. (h) Spivey,
A. C.; Maddaford, A.; Fekner, T.; Redgrave, A. J.;
Frampton, C. S. J. Chem. Soc., Perkin Trans. 1 2000, 3460.
(i) Naraku, G.; Shimomoto, N.; Hanamoto, T.; Inanaga, J.
Enantiomer 2000, 5, 135. (j) Kawabata, T.; Yamamoto, K.;
Momose, Y.; Yoshida, H.; Nagaoka, Y.; Fuji, K. Chem.
Commun. 2001, 2700. (k) Jeong, K.-S.; Kim, S.-H.; Park,
H.-J.; Chang, K.-J.; Kim, K. S. Chem. Lett. 2002, 1114.
(l) Priem, G.; Anson, M. S.; Macdonald, S. J. F.; Pelotier, B.;
Campbell, I. B. Tetrahedron Lett. 2002, 43, 6001.
2
2
2
R1
N
R
R
I–
Me
O
R2
–Cl
1a R = COHPh2
R = CNMe2Ph2
21 R = H
1aMe R = COHPh2
8Me R = CNMe2Ph2
21Me R = H
1aAc R1 = COHPh2
R2 = CHMe2
8
8Ac R1 = CNMe2Ph2
R2 = Me
21Ac R1 = H
R2 = CHMe2
Entry Cat.
δH-2a,b,c
δH-5a,b,c
δH-6a,b,c
8.09
δCH3/HCR2
1
2
3
4
5
6
7
8
9d
1a
7.33
6.45
–
1aMe 6.52 (–0.81) 6.80 (0.45) 8.04 (–0.05) 3.88
1aAc 8.06 (0.73)
8.26
8Me 7.71 (–0.53) 6.97 (0.49) 8.43 (0.28)
7.15 (0.70) 9.10 (1.01)
4.14
–
8
6.48 8.15
(m) Seitzberger, J. G.; Dissing, C.; Søtofte, I.; Norrby, P.-O.;
Johannsen, M. J. Org. Chem. 2005, 70, 8332. (n) Yamada,
S.; Misono, T.; Iwai, Y. Tetrahedron Lett. 2005, 46, 2239.
(o) Poisson, T.; Penhoat, M.; Papamical, C.; Dupas, G.;
Dalla, V.; Marsais, F.; Levacher, V. Synlett 2005, 2285.
(p) Nguyen, H. V.; Butler, D. C. D.; Richards, C. J. Org.
Lett. 2006, 8, 769. (q) Nguyen, H. V.; Motevalli, M.;
Richards, C. J. Synlett 2007, 725.
4.17
8Ac
21
8.24 (–0.02) 6.68 (0.20) 8.06 (–0.09) 2.25
8.19
6.47
8.16
–
21Me 8.17 (–0.02) 6.90 (0.43) 8.21 (0.05)
21Ac 8.72 (0.53) 7.32 (0.85) 9.32 (1.16)
4.21
4.11
(6) For examples, see: (a) Miller, S. J.; Copeland, G. T.;
Papaioannou, N.; Horstmann, T. E.; Ruel, E. M. J. Am.
Chem. Soc. 1998, 120, 1629. (b) Jarvo, E. R.; Copeland, G.
T.; Papaioannou, N.; Bonitatebus, P. J.; Miller, S. J. J. Am.
Chem. Soc. 1999, 121, 11638. (c) Jarvo, E. R.; Vasbinder,
M. M.; Miller, S. J. Tetrahedron 2000, 56, 9773.
a The δ value is quoted in ppm in CDCl3 as solvent.
b Value in parenthesis represents Δδ: the change in chemical shift of
the proton indicated on methylation or acylation (in ppm), a negative
value for Δδ indicates an upfield shift.
c All pyridine ring proton resonances were unambiguously assigned
by NMR spectroscopy (1H–1H COSY, 1H–13C COSY, NOE and 1-D
TOCSY experiments).
(d) Vasbinder, M. M.; Jarvo, E. R.; Miller, S. J. Angew.
Chem. Int. Ed. 2001, 40, 2824. (e) Ishihara, K.; Kosugi, Y.;
Akakura, M. J. Am. Chem. Soc. 2004, 126, 12212.
(f) Hrdina, R.; Müller, C. E.; Schreiner, P. R. Chem.
Commun. 2010, 46, 2689.
this phenomenon further and to determine the precise
mode of action of 8 are underway.
(7) For representative examples, see: (a) Birman, V. B.;
Uffman, E. W.; Jiang, H.; Li, X.; Kilbane, C. J. J. Am. Chem.
Soc. 2004, 126, 12226. (b) Birman, V. B.; Jiang, H. Org.
Lett. 2005, 7, 3445. (c) Li, X.; Liu, P.; Houk, K. N.; Birman,
V. B. J. Am. Chem. Soc. 2008, 130, 13836. (d) Birman, V.
B.; Li, X. Org. Lett. 2008, 10, 1115. (e) Zhang, Y.; Birman,
V. B. Adv. Synth. Catal. 2009, 351, 2525. (f) Hu, B.; Meng,
M.; Wang, Z.; Du, W.; Fossey, J. S.; Hu, X.; Deng, W.-P. J.
Am. Chem. Soc. 2010, 132, 17041.
Acknowledgment
We thank the Science Foundation Ireland for financial support.
Supporting Information for this article is available online at
m
iotSrat
ungIifoop
r
t
(8) For representative examples, see: (a) Oriyama, T.; Hori, Y.;
Imai, K.; Sasaki, R. Tetrahedron Lett. 1996, 37, 8543.
(b) Oriyama, T.; Imai, K.; Hosoya, T.; Sano, T. Tetrahedron
Lett. 1998, 39, 397. (c) Oriyama, T.; Imai, K.; Sano, T.;
Hosoya, T. Tetrahedron Lett. 1998, 39, 3529.
(9) For representative examples, see: (a) Suzuki, Y.; Yamauchi,
K.; Muramatsu, K.; Sato, M. Chem. Commun. 2004, 2770.
(b) Suzuki, Y.; Muramatsu, K.; Yamauchi, K.; Morie, Y.;
Sato, M. Tetrahedron 2006, 62, 302. (c) Kano, T.; Sasaki,
K.; Maruoka, K. Org. Lett. 2005, 7, 1347.
References and Notes
(1) For selected reviews, see: (a) Chen, C.-S.; Sih, C. Angew.
Chem. Int. Ed. 1989, 28, 695. (b) Theil, F. Chem. Rev. 1995,
95, 2203.
(2) For recent reviews, see: (a) Connon, S. J. Lett. Org. Chem.
2006, 3, 333. (b) Wurz, R. P. Chem. Rev. 2007, 107, 5570.
(c) Denmark, S. E.; Beutner, G. L. Angew. Chem. Int. Ed.
2008, 47, 1560. (d) Spivey, A. C.; Arseniyadis, S. Top. Curr.
Chem. 2010, 291, 233. (e) Müller, C. E.; Schreiner, P. R.
Angew. Chem. Int. Ed. 2011, 50, 6012. (f) Pellissier, H. Adv.
Synth. Catal. 2011, 353, 1613.
(10) (a) O’Dálaigh, C.; Hynes, S. J.; Maher, D. J.; Connon, S. J.
Org. Biomol. Chem. 2005, 3, 981. (b) O’Dálaigh, C.; Hynes,
S. J.; O’Brien, J. E.; McCabe, T.; Maher, D. J.; Watson, G.
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Synlett 2013, 24, 1728–1734