Lang et al.
JOCArticle
For example, Lectka’s bifunctional systems using In(III) in com-
bination with cinchona alkaloid catalyzed the formation of
β-lactams where the tertiary amine attacked a ketene to form
an enolate nucleophile, and In(III) activated the imino ester
electrophile (Figure 1C).11a Currently, only several successful
examples of covalently bonded metal/amine catalysts have
been developed and systematically studied in asymmetric
catalysis,11 because metal/base bifunctional catalysts are chal-
lenging to achieve: one difficulty is that the acid and base tend
to sequester each other and lose activity.1b
As a part of our research program directed toward devel-
opment of dinuclear/bifunctional catalysts,7a we envisioned
a series of novel dual activation catalysts (either bimetallic or
bifunctional catalysts) could be developed taking advantage
of facile functionalization of the central nitrogen of the aza-
bis(oxazoline) (aza-Box) units (Figure 2). As privileged
chiral ligands,13 bis(oxazoline) and its related structures such
as pyBox and bora-Box have been well studied for a broad
variety of enantioselective reactions.14 Among these ligands,
aza-Box was successfully developed by Reiser and exhibited
high activity for a number of asymmetric transformations
including cyclopropanation reactions, kinetic resolutions of
1,2-diols, conjugate reduction of R,β-unsaturated carbonyl
compounds, and Michael additions of indole.15 Importantly,
Reiser and co-workers nicely developed recyclable cata-
lysts by immobilizing aza-Box ligands on polymeric support
or nanoparticles through alkylation of the central nitro-
gen.16a-d Recently, Garcıa and co-workers developed a
new self-supported Cu coordination polymer catalyst based
on a ditopic chiral ligand bearing two aza-Box units for
(3) For review on dinucleating ligand design, see: (a) Gavrilova, A. L.;
Bosnich, B. Chem. Rev. 2004, 104, 349–383. For examples of bimetallic
asymmetric catalysts, see: (b) Handa, S.; Gnanadesikan, V.; Matsunaga, S.;
Shibasaki, M. J. Am. Chem. Soc. 2007, 129, 4900–4901. (c) Handa, S.;
Nagawa, K.; Sohtome, Y.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int.
Ed. 2008, 47, 3230–3233. (d) Chen, Z.; Morimoto, H.; Matsunaga, S.;
Shibasaki, M. J. Am. Chem. Soc. 2008, 130, 2170–2171. (e) Handa, S.;
Gnanadesikan, V.; Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2010,
132, 4925–4934. (f) Mouri, S.; Chen, Z.; Mitsunuma, H.; Furutachi, M.;
Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2010, 132, 1255–1257.
(4) (a) Konsler, R. G.; Karl, J.; Jacobsen, E. N. J. Am. Chem. Soc. 1998,
120, 10780–10781. (b) Annis, D. A.; Jacobsen, E. N. J. Am. Chem. Soc. 1999,
121, 4147–4154. (c) Breinbauer, R.; Jacobsen, E. N. Angew. Chem., Int. Ed.
2000, 39, 3604–3607. (d) Ready, J. M.; Jacobsen, E. N. J. Am. Chem. Soc.
2001, 123, 2687–2688. (e) Ready, J. M.; Jacobsen, E. N. Angew. Chem., Int.
Ed. 2002, 41, 1374–1377. (f) Sammis, G. M.; Danjo, H.; Jacobsen, E. N.
J. Am. Chem. Soc. 2004, 126, 9928–9929. (g) Mazet, C.; Jacobsen, E. N.
Angew. Chem., Int. Ed. 2008, 47, 1762–1765.
(5) (a) Trost, B. M.; Ito, H. J. Am. Chem. Soc. 2000, 122, 12003–12004. (b)
Trost, B. M.; Ito, H.; Silcoff, E. R. J. Am. Chem. Soc. 2001, 123, 3367–3368.
(c) Trost, B. M.; Yeh, V. S. C. Angew. Chem., Int. Ed. 2002, 41, 861–863. (d)
Trost, B. M.; Terrell, L. R. J. Am. Chem. Soc. 2003, 125, 338–339. (e) Trost,
B. M.; Fettes, A.; Shireman, B. T. J. Am. Chem. Soc. 2004, 126, 2660–2661. (f)
Trost, B. M.; Shin, S.; Sclafini, J. A. J. Am. Chem. Soc. 2005, 127, 8602–8603.
(g) Trost, B. M.; Weiss, A. H.; von Wangelin, A. J. J. Am. Chem. Soc. 2006,
128, 8–9. (h) Trost, B. M.; Jaratjaroonphong, J.; Reutrakul, V. J. Am. Chem.
Soc. 2006, 128, 2778–2779. (i) Trost, B. M.; Hisaindee, S. Org. Lett. 2006, 8,
6003–6005. (j) Trost, B. M.; Lupton, D. W. Org. Lett. 2007, 9, 2023–2026.
(6) (a) DiMauro, E. F.; Kozlowski, M. C. J. Am. Chem. Soc. 2002, 124,
12668–12669. (b) Fennie, M. W.; DiMauro, E. F.; O’Brien, E. M.;
Annamalai, V.; Kozlowski, M. C. Tetrahedron 2005, 61, 6249–6265.
(7) (a) Park, J.; Lang, K.; Abboud, K. A.; Hong, S. J. Am. Chem. Soc.
2008, 130, 16484–16485. (b) Gianneschi, N. C.; Bertin, P. A.; Nguyen, S. T.;
Mirkin, C. A.; Zakharov, L. N.; Rheingold, A. L. J. Am. Chem. Soc. 2003,
125, 10508–10509. (c) Gianneschi, N. C.; Cho, S.-H.; Nguyen, S. T.; Mirkin,
C. A. Angew. Chem., Int. Ed. 2004, 43, 5503–5507. (d) Zheng, X.; Jones,
C. W.; Weck, M. Chem.;Eur. J. 2006, 12, 576–583. (e) Holbach, M.; Weck,
M. J. Org. Chem. 2006, 71, 1825–1836. (f) Zheng, X.; Jones, C. W.; Weck, M.
J. Am. Chem. Soc. 2007, 129, 1105–1112.
(11) For examples of covalently bonded metal/amine catalysts, see: (a)
France, S.; Shah, M. H.; Weatherwax, A.; Wack, H.; Roth, J. P.; Lectka, T.
J. Am. Chem. Soc. 2005, 127, 1206–1215. (b) Paull, D. H.; Scerba, M. T.;
Alden-Danforth, E.; Widger, L. R.; Lectka, T. J. Am. Chem. Soc. 2008, 130,
17260–17261. (c) Abraham, C. J.; Paull, D. H.; Bekele, T.; Scerba, M. T.;
Dudding, T.; Lectka, T. J. Am. Chem. Soc. 2008, 130, 17085–17094. (d) Lin,
Y.-M.; Boucau, J.; Li., Z.; Casarotto, V.; Lin, J.; Nguyen, A. N.;
Ehrmantraut, J. Org. Lett. 2007, 9, 567–570. (e) Tiseni, P. S.; Peters, R.
Org. Lett. 2008, 10, 2019–2022. (f) Yang, F.; Wei, S.; Chen, C.-A.; Xi, P.;
Yang, L.; Lan, J.; Gau, H.-M.; You, J. Chem.;Eur. J. 2008, 14, 2223–2231.
(g) Xu, Z.; Daka, P.; Wang, H. Chem. Commun. 2009, 6825–6827. (h)
Chidara, S.; Lin, Y.-M. Synlett 2009, 1675–1679.
(12) For examples of linked metal/Lewis base catalysts, see: (a) Ichikawa,
E.; Suzuki, M.; Yabu, K.; Albert, M.; Kanai, M.; Shibasaki, M. J. Am. Chem.
Soc. 2004, 126, 11808–11809. (b) Kanai, M.; Kato, N.; Ichikawa, E.;
Shibasaki, M. Pure Appl. Chem. 2005, 77, 2047–2052. (c) Hatano, M.;
Miyamoto, T.; Ishihara, K. J. Org. Chem. 2006, 71, 6474–6484. For selective
examples for separate Lewis acid/amine catalysts, see: (d) Abell, J. P.;
Yamamoto, H. J. Am. Chem. Soc. 2009, 131, 15118–15119. (e) Lundgren,
S.; Wingstrand, E.; Penhoat, M.; Moberg, C. J. Am. Chem. Soc. 2005, 127,
11592–11593. (f) Palomo, C.; Oiarbide, M.; Laso, A. Angew. Chem., Int. Ed.
2005, 44, 3881–3884. (g) Yang, F.; Zhao, D.; Lan, J.; Xi, P.; Yang, L.; Xiang,
S.; You, J. Angew. Chem., Int. Ed. 2008, 47, 5646–5649. (h) Kowalczyk, R.;
(8) For other examples of dinuclear catalyst application, see: (a) Li, L.;
Metz, M. V.; Li, H.; Chen, M.-C.; Marks, T. J.; Liable-Sands, L.; Rheingold,
ꢀ
A. L. J. Am. Chem. Soc. 2002, 124, 12725–12741. (b) Motta, A.; Fragala,
I. L.; Marks, T. J. J. Am. Chem. Soc. 2009, 131, 3974–3984. (c) Braune, W.;
Okuda, J. Angew. Chem., Int. Ed. 2003, 42, 64–68. (d) Moore, D. R.; Cheng,
M.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc. 2003, 125, 11911–
11924. (e) Lee, B. Y.; Kwon, H. Y.; Lee, S. Y.; Na, S. J.; Han, S. I.; Yun, H.;
Lee, H.; Park, Y.-W. J. Am. Chem. Soc. 2005, 127, 3031–3037. (f) Hirahata,
W.; Thomas, R. M.; Lobkovsky, E. B.; Coates, G. W. J. Am. Chem. Soc.
2008, 130, 17658–17659.
_
Kwiatkowski, P.; Skarzewski, J.; Jurczak, J. J. Org. Chem. 2009, 74, 753–756.
(9) For review on bifunctional organocatalysts, see: (a) Connon, S. J.
Chem. Commun. 2008, 2499–2510. (b) Marcelli, T.; van Maarseveen, J. H.;
Hiemstra, H. Angew. Chem., Int. Ed. 2006, 45, 7496–7504. (c) Connon, S. J.
Angew. Chem., Int. Ed. 2006, 45, 3909–3912. For selected examples of
bifunctional organocatalysts, see: (d) Taylor, M. S.; Jacobsen, E. N. Angew.
Chem., Int. Ed. 2006, 45, 1520–1543. (e) Zuend, S, J.; Jacobsen, E. N. J. Am.
Chem. Soc. 2007, 129, 15872–15883. (f) Rabalakos, C.; Wulff, W. D. J. Am.
Chem. Soc. 2008, 130, 13524–13525. (g) Li, D. R.; Murugan, A.; Falck, J. R.
J. Am. Chem. Soc. 2008, 130, 46–48. (h) Fang, Y.-Q.; Jacobsen, E. N. J. Am.
Chem. Soc. 2008, 130, 5660–5661. (i) Malerich, J. P.; Hagihara, K.; Rawal,
V. H. J. Am. Chem. Soc. 2008, 130, 14416–14417. (j) Singh, A.; Johnston,
J. N. J. Am. Chem. Soc. 2008, 130, 5866–5867. (k) Oh, S. H.; Rho, H. S.; Lee,
J. W.; Lee, J. E.; Youk, S. H.; Chin, J.; Song, C. E. Angew. Chem., Int. Ed.
2008, 47, 7872–7875. (l) Abermil, N.; Masson, G.; Zhu, J. J. Am. Chem. Soc.
2008, 130, 12596–12597. (m) Wang, X.; Chen, Y.-F.; Niu, L.-F.; Xu, P.-F.
Org. Lett. 2009, 11, 3310–3313. (n) Kang, Y. K.; Kim, D. Y. J. Org. Chem.
2009, 74, 5734–5737. (o) Yu, Z.; Liu, X.; Zhou, L.; Lin, L.; Feng, X. Angew.
Chem., Int. Ed. 2009, 48, 5195–5198. (p) Han, X.; Kwiatkowski, J.; Xue, F.;
Huang, K.-W.; Lu, Y. Angew. Chem., Int. Ed. 2009, 48, 7604–7607. (q) Li,
D. R.; He, A.; Falck, J. R. Org. Lett. 2010, 12, 1756–1759.
(i) Zulauf, A.; Mellah, M.; Schulz, E. J. Org. Chem. 2009, 74, 2242–2245. (j)
Breuning, M.; Hein, D.; Steiner, M.; Gessner, V. H.; Strohmann, C. Chem.;
Eur. J. 2009, 15, 12764–12769. (k) Selvakumar, S.; Sivasankaran, D.; Singh,
V. K. Org. Biomol. Chem. 2009, 7, 3156–3162. (l) Wang, W.; Shen, K.; Hu,
X.; Wang, J.; Liu, X.; Feng, X. Synlett 2009, 1655–1658. (m) Noole, A.;
Lippur, K.; Metsala, A.; Lopp, M.; Kanger, T. J. Org. Chem. 2010, 75, 1313–
1316. (n) Steurer, M.; Bolm, C. J. Org. Chem. 2010, 75, 3301–3310. (o) Lee,
J.-M.; Kim, J.; Shin, Y.; Yeom, C.-E.; Lee, J. E.; Hyeon, T.; Kim, B. M.
Tetrahedron: Asymmetry 2010, 21, 285–291.
(13) (a) Yoon, T. P.; Jacobsen, E. N. Science 2003, 299, 1691–1693.
(b) Hargaden, G. C.; Guiry, P. J. Chem. Rev. 2009, 109, 2505–2550.
(14) (a) Johnson, J. S.; Evans, D. A. Acc. Chem. Res. 2000, 33, 325–335.
(b) Rechavi, D.; Lemaire, M. Chem. Rev. 2002, 102, 3467–3494. (c) Desimoni, G.;
Faita, G.; Quadrelli, P. Chem. Rev. 2003, 103, 3119–3154. (d) McManus, H. A.;
€
Guiry, P. J. Chem. Rev. 2004, 104, 4151–4202. (e) Mazet, C.; Kohler, V.; Pfaltz,
A. Angew. Chem., Int. Ed. 2005, 44, 4888–4891. (f) Desimoni, G.; Faita, G.;
Jørgensen, K. A. Chem. Rev. 2006, 106, 3561–3651. (g) Sun, Z.; Yu, S.; Ding, Z.;
Ma, D. J. Am. Chem. Soc. 2007, 129, 9300–9301. (h) Zocher, E.; Dietiker, R.;
Chen, P. J. Am. Chem. Soc. 2007, 129, 2476–2481.
(15) (a) Glos, M.; Reiser, O. Org. Lett. 2000, 2, 2045–2048. (b) Werner,
H.; Vicha, R.; Gissibl, A.; Reiser, O. J. Org. Chem. 2003, 68, 10166–10168. (c)
Fraile, J. M.; Garcıa, J. I.; Herrerıas, C. I.; Mayoral, J. A.; Reiser, O.;
(10) (a) Okino, T.; Hoashi, Y.; Takemoto, Y. J. Am. Chem. Soc. 2003,
125, 12672–12673. (b) Okino, T.; Hoashi, Y.; Furukawa, T.; Xu, X.;
Takemoto, Y. J. Am. Chem. Soc. 2005, 127, 119–125. (c) Hamza, A.;
ꢁ
Socuellamos, A.; Werner, H. Chem.;Eur. J. 2004, 10, 2997–3005. (d)
ꢁ
ꢁ
Schubert, G.; Soos, T.; Papai, I. J. Am. Chem. Soc. 2006, 128, 13151–
13160. (d) Yamaoka, Y.; Miyabe, H.; Takemoto, Y. J. Am. Chem. Soc.
2007, 129, 6886–6887.
Geiger, C.; Kreitmeier, P.; Reiser, O. Adv. Synth. Catal. 2005, 347, 249–
254. (e) Rasappan, R.; Hager, M.; Gissibl, A.; Reiser, O. Org. Lett. 2006, 8,
6099–6102.
J. Org. Chem. Vol. 75, No. 19, 2010 6425