3432, 3303, 1655, 1591, 1522, 1322, 1159, 1059. ESI HRMS calcd.
for C33H35N3O5S + H 586.2375, found 586.2351.
2 For reviews, see: (a) D. Sinou, Adv. Synth. Catal., 2002, 344, 221; (b)
C.-J. Li, Acc. Chem. Rev., 2002, 35, 533; (c) K. H. Shaughnessy and
R. B. DeVasher, Curr. Org. Chem., 2005, 9, 585; (d) N. E. Leadbeater,
Chem. Commun., 2005, 2881.
1
(R,R)-1b. Yield 91%. [a]2D3 +11.3 (c = 0.24, THF). H NMR
3 For reviews, see: (a) J. P. Geneˆt and M. Savignac, J. Organomet. Chem.,
(CDCl3, 300 MHz) d 0.87–2.14 (m, 8H), 2.75–2.87 (m, 1H),
3.20–3.35 (m, 1H), 4.89, 5.05 (s × 2, 12H), 6.49–6.74 (m, 9H),
7.28–7.45 (m, 20H), 7.89–8.04 (m, 4H) ppm. Partial 13C NMR
(CDCl3 + DMSO, 75 MHz) d 29.2, 29.7, 31.5, 36.8, 37.8, 59.1,
63.8, 74.6, 106.2, 110.2, 111.2, 111.8, 112.0, 125.0, 132.3, 132.7,
133.3, 140.9, 141.5, 143.8, 147.7, 164.4, 164.8, 170.8 ppm. IR (KBr)
m (cm−1): 3437, 1658, 1594, 1321, 1157, 1054. ESI HRMS calcd.
for C61H59N3O9S + H 1010.4050, found 1010.4095.
´
1999, 576, 305; (b) F. Joo´ and A Katho´, J. Mol. Catal. A: Chem., 1997,
116, 3; For recent examples, see: (c) S. H. Hong and R. H. Grubbs,
J. Am. Chem. Soc., 2006, 128, 3508 (d) J. P. Gallivan, J. P. Jordan and
R. H. Grubbs, Tetrahedron Lett., 2005, 46, 2577 (e) L. R. Moore and
K. H. Shaughnessy, Org. Lett., 2004, 6, 225.
4 For pioneering works of Noyori and Ikariya on this catalytic system,
see: (a) S. Hashiguchi, A. Fujii, J. Takehara, T. Ikariya and R. Noyori,
J. Am. Chem. Soc., 1995, 117, 7562; (b) A. Fujii, S. Inoue, S. Hishiguchi,
N. Uemastu, T. Ikariya and R. Noyori, J. Am. Chem. Soc., 1996, 118,
2521; (c) N. Uematsu, A. Fujii, S. Hashiguchi, T. Ikariya and R. Noyori,
J. Am. Chem. Soc., 1996, 118, 4916; (d) K. Matsumura, S. Hashiguchi,
T. Ikariya and R. Noyori, J. Am. Chem. Soc., 1997, 119, 8738; (e) S.
Hashiguchi, A. Fujii, K. J. Haack, K. Matsumura, T. Ikariya and R.
Noyori, Angew. Chem., Int. Ed. Engl., 1997, 36, 288; (f) K. J. Haack,
S. Hashiguchi, A. Fujii, T. Ikariya and R. Noyori, Angew. Chem., Int.
Ed. Engl., 1997, 36, 285; (g) R. Noyori and S. Hashiguchi, Acc. Chem.
Res., 1997, 30, 97.
5 For recent developments, see: (a) D. S. Matharu, D. J. Morris, A. M.
Kawamoto, G. J. Clarkson and M. Wills, Org. Lett., 2005, 7, 5489;
(b) F. K. Cheung, A. M. Hayes, J. Hannedouche, A. S. Y. Yim and M.
Wills, J. Org. Chem., 2005, 70, 3188; (c) A. M. Hayes, D. J. Morris, G. J.
Clarkson and M. Wills, J. Am. Chem. Soc., 2005, 127, 7318; (d) R. W.
Guo, C. Elpelt, X. H. Chen, D. T. Song and R. H. Morris, Chem.
Commun., 2005, 3050; (e) W. Baratta, E. Herdtweck, K. Siega, M.
Toniutti and P. Rigo, Organometallics, 2005, 24, 1660; (f) J. B. Sortais,
V. Ritleng, A. Voelklin, A. Houluigue, H. Smail, L. Barloy, C. Sirlin,
G. K. M. Verzijl, J. A. F. Boogers, A. H. M. De Vries, J. G. De Vries and
M. Pfeffer, Org. Lett., 2005, 7, 1247; (g) J. Hannedouche, G. J. Clarkson
and M. Wills, J. Am. Chem. Soc., 2004, 126, 986; (h) A. Schlatter, M.
Kundu and W. D. Woggon, Angew. Chem., Int. Ed., 2004, 43, 6731;
(i) For a recent review, see: S. Gladiali and E. Alberico, Chem. Soc.
Rev., 2006, 35, 226.
1
(R,R)-1c. Yield 90%. [a]2D3 +3.4 (c = 0.30, THF). H NMR
(CDCl3, 300 MHz) d 0.89–1.72 (m, 8H), 2.94–2.99 (m, 1H), 3.32–
3.42 (m, 1H), 4.79–5.03 (m, 28H), 6.48–6.67 (m, 21H), 7.13–
7.38 (m, 40H), 7.75–7.90 (m, 4H) ppm. IR (KBr) m (cm−1):
3433, 3031, 1599, 1450, 1321, 1157, 1053. ESI HRMS calcd. for
C117H107N3O17S + H 1858.7395, found 1858.7390.
1
(R,R)-1d. Yield 85%. [a]2D3 +1.3 (c = 0.31, THF). H NMR
(CDCl3, 300 MHz) d 4.79–5.0 (m, 60H), 6.48–6.67 (m, 45H), 7.25–
7.38 (m, 84H) ppm. The signal of the DACH moiety is too small
to be detected. IR (KBr) m (cm−1): 3411, 3032, 1595, 1449, 1374,
1157, 1052. MALDI-TOF MS calcd. for C229H203N3O33S + K 3593,
found 3593.
General procedure for asymmetric transfer hydrogenation of
ketone compounds
[Cp*RhCl2]2 (1.3 mg, 0.002 mmol), dendritic ligand
1
6 (a) X. F. Wu, X. G. Li, W. Hems, F. King and J. L. Xiao, Org. Biomol.
Chem., 2004, 2, 1818; (b) X. G. Li, X. F. Wu, W. P. Chen, F. E. Hancock,
F. King and J. L. Xiao, Org. Lett., 2004, 6, 3321; (c) X. F. Wu, X. G.
Li, F. King and J. L. Xiao, Angew. Chem., Int. Ed., 2005, 44, 3407;
(d) X. Wu, D. Vinci, T. Ikariya and J. Xiao, Chem. Commun., 2005,
4447; (e) C. Letondor, N. Humbert and T. R. Ward, Proc. Natl. Acad.
Sci. U. S. A., 2005, 102, 4683; (f) P. N. Liu, J. G. Deng, Y. Q. Tu and
S. H. Wang, Chem. Commun., 2004, 2070; (g) Y. P. Ma, H. Liu, L.
Chen, X. Cui, J. Zhu and J. G. Deng, Org. Lett., 2003, 5, 2103; (h) F.
Wang, H. Liu, L. Cun, J. Zhu, J. Deng and Y. Jiang, J. Org. Chem.,
2005, 70, 9424; (i) Y. Himeda, N. Onozawa-Komatsuzaki, H. Sugihara,
H. Arakawa and K. Kasuga, J. Mol. Catal. A: Chem., 2003, 195, 95;
(j) H. Y. Rhyoo, H. J. Park, W. H. Suh and Y. K. Chung, Tetrahedron
Lett., 2002, 43, 269; (k) T. Thorpe, J. Blacker, S. M. Brown, C. Bubert, J.
Crosby, S. Fitzjohn, J. P. Muxworthy and J. M. J. Williams, Tetrahedron
Lett., 2001, 42, 4037; (l) J. Canivet, G. Labat, H. Stoeckli-Evans and
G. Su¨ss-Fink, Eur. J. Inorg. Chem., 2005, 4493.
(0.0044 mmol) and NEt3 (2 lL, 0.013 mmol) were stirred in
DCM at 40 ◦C for 1 h. After removal of DCM under reduced
pressure, ketone 7 (0.4 mmol), HCOONa (250 mg, 6 equiv.) and
water (1 mL) were added. After the reaction was completed
(monitored by TLC), the reaction mixture was extracted with
ether. The organic phase was dried over anhydrous Na2SO4 and
concentrated under reduced pressure. The product was directly
used for GC analysis. Products from 7h, 7j and 7k were purified
by flash chromatography on silica gel and the ees were determined
by HPLC analysis on OD or AS column.
General procedure for recycling of dendritic catalyst in asymmetric
transfer hydrogenation of acetophenone
7 J. Wu, F. Wang, Y. Ma, X. Cui, L. Cun, J. Zhu, J. Deng and B. Yu,
Chem. Commun., 2006, 1766.
[Cp*RhCl2]2 (6.5 mg, 0.01 mmol), dendritic ligand 1b
(0.022 mmol) and NEt3 (10 lL, 0.065 mmol) were stirred in DCM
at 40 ◦C for 1 h. After removal of DCM under reduced pressure,
acetophenone (0.24 mL, 2 mmol), HCOONa (1.25 g, 12 mmol)
and water (5 mL) were added. After a specific reaction time, n-
hexane (5 mL) was added to precipitate the dendritic catalyst,
and the organic phase containing the chiral alcohol was carefully
removed. Before the next reaction could be conducted, HCOOH
(80 lL, 2 mmol) was added to adjust the pH value of aqueous
solution to about 7. Then acetophenone (2 mmol) were added and
the mixture was stirred at 40 ◦C.
8 Ru–TsDACH catalysed ATH: (a) K. Puntener, L. Schwink and P.
Knochel, Tetrahedron Lett., 1996, 37, 8165; (b) H. Matsunaga, T.
Ishizuka and T. Kunieda, Tetrahedron Lett., 2005, 46, 3645; (c) G. J.
Kim, S. H. Kim, P. H. Chong and M. A. Kwon, Tetrahedron Lett.,
2002, 43, 8059; (d) C. M. Marson and I. Schwarz, Tetrahedron Lett.,
2000, 41, 8999; (e) Rh/Ir–TsDACH catalysed ATH: K. Murata, T.
Ikariya and R. Noyori, J. Org. Chem., 1999, 64, 2186; (f) ref. 6d
and 6l.
9 (a) Y.-C. Chen, T.-F. Wu, J.-G. Deng, H. Liu, Y.-Z. Jiang, M. C. K.
Choi and A. S. C. Chan, Chem. Commun., 2001, 1488; (b) Y.-C. Chen,
T.-F. Wu, J.-G. Deng, H. Liu, X. Cui, J. Zhu, Y.-Z. Jiang, M. C. K.
Choi and A. S. C. Chan, J. Org.Chem., 2002, 67, 5301; (c) Y.-C. Chen,
T.-F. Wu, L. Jiang, J.-G. Deng, H. Liu, J. Zhu and Y.-Z. Jiang, J. Org.
Chem., 2005, 70, 1006; (d) W. Liu, X. Cui, L. Cun, J. Zhu and J. Deng,
Tetrahedron: Asymmetry, 2005, 16, 2525.
10 For recent reviews on dendritic catalysts, see: (a) J. N. H. Reek, D. de
Groot, G. E. Oosterom, P. C. J. Kamer and P. W. N. M. van Leeuwen,
Rev. Mol. Biotechnol., 2002, 90, 159; (b) L. J. Twyman, A. S. H. King
and I. K. Martin, Chem. Soc. Rev., 2002, 31, 69; (c) Q.-H. Fan, Y.-M. Li
References
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Org. Biomol. Chem., 2006, 4, 3319–3324 | 3323
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