Cooperativity in Asymmetric
Bimetallic Catalysis
05/20/2015
Presented By Michael C. Young
Strategies for Bimetallic Catalysis
There are numerous intramolecular and intermolecular methods to achieve bi-metallic catalysis:
•
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Pioneering Work
Allylation of activated methylene compounds had originally been difficult to achieve good ee with
chiral phosphine ligands.
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i) NaH/THF; ii) allylacetate/[(allyl)PdCl]2 / -30 ºC
80%, 45% ee (S)
Hayashi, T.; Kanehira, K.; Tsuchiya, H.; Kumada, M. Chem. Commun., 1982, 2586.
64%, 31% ee (S)
86%, 15% ee (S)
Improved Allylation Protocol (I)
Kumada group investigated improving the ee with a new class of chiral phosphine.
•
Hayashi, T.; Kanehira, K.; Hagihara, T.; Kumada, M. J. Org. Chem., 1988, 113.
Improved Allylation Protocol (II)
Replacing H-bonding with metal chelation changes solvent preference as well as stereoselectivity.
•
Sawamura, M.; Nagata, H.; Sakamoto, H.; Ito, Y. J. Am. Chem. Soc., 1992, 194, 2586.
Bifunctional Asymmetric Nitro Allylation
Ito and coworkers hoped that they could better understand their catalyst in another
transformation.
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Base
Base
Solvent
R-Group
Conc.
Add.
Yield (%)
(%)
Yield
ee %
%
ee
KF
Mesitylene
Me
1.0
N/AM
40
43
14
23 (R)
KF
Toluene
Et
1.0
N/AM
47
44
19
37 (R)
KF
THF
t-Bu
1.0
N/AM
66
95
25 (R)
51
KF
RbF
CH
t-Bu
2Cl2
1.0
N/AM
33
95
25
60 (R)
(R)
RbF
CsF
THF
t-Bu
1.0
N/AM
50
91
29 (R)
(R)
34
RbF
CH
t-Bu
2Cl2
1.0 M4
RbClO
57
98
38
69 (R)
RbF
CH
t-Bu
2Cl2
0.5 M4*
RbClO
28
92
42
80 (R)
CsF
CH2Cl2
1.0 M
31
31 (R)
Sawamura, M.; Nakayama, Y.; Tang, W.-M.; Ito, Y. J. Org. Chem., 1996, 61, 9090.
Trost Ligand as a Bifunctional Ligand
Trost, B. M.; Radinov, R. J. Am. Chem. Soc., 1997, 199, 2586.
Asymmetric Carbonyl Alkylation (I)
Aldehyde
Zinc
Solvent
Time (h)
Yield (%)
ee (%) – (S)
C6H5
(C2H5)2Zn
PhMe
6
97
98
C6H5
(C2H5)2Zn
Hexanes-PhMe
6
94
98
C6H5
(C2H5)2Zn
Et2O-PhMe
6
98
99
C6H5
(C2H5)2Zn
THF-PhMe
64
44
91
C6H5
(CH3)2Zn
PhMe
70
59
91
P-ClC6H4
(C2H5)2Zn
PhMe
12
86
93
(E)-C6H5CHCH
(C2H5)2Zn
PhMe
6
81
96
C6H5CH2CH2
(C2H5)2Zn
PhMe
12
80
90
N-C6H13
(C2H5)2Zn
PhMe
24
81
61
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Kitamura, M.; Suga, S.; Kawai, K.; Noyori, R. J. Am. Chem. Soc., 1986, 108, 6072.
Asymmetric Carbonyl Alkylation (II)
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
DiMauro, E. F.; Kozlowski, M. C. Org. Lett., 2001, 3, 3053.
Asymmetric Carbonyl Alkylation (III)
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Funabashi, K.; Jachmann, M.; Kanai, M.; Shibasaki, M. Angew. Chem., Int. Ed., 2003, 42, 5489.
Shibasaki-BINOL Chemistry
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Shibasaki, M.; Kanai, M.; Matsunaga, S.; Kumagai, N. Acc. Chem. Res., 2009, 42, 1117.
Sasai, H.; Suzuki, T.; Arai, S.; Arai, T.; Shibasaki, M. J. Am. Chem. Soc., 1992, 114, 4418.
Arai, T.; Sasai, H.; Aoe, K.-I.; Okamura, K.; Date, T.; Shibasaki, M. Angew. Chem., Int. Ed., 1996, 35, 104.
Asymmetric Strecker-Type Reactions
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Masumoto, S.; Usuda, H.; Suzuki, M.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc., 2003, 125, 5634.
Kanai, M.; Kato, N.; Ichikawa, E.; Shibasaki, M. Synlett, 2005, 1491.
Kato, N. et al. J. Am. Chem. Soc., 2006, 128, 16438.
Catalytic Asymmetric Aldol Reactions
Trost, B. M.; Ito, H. J. Am. Chem. Soc., 2000, 122, 12003.
Diol Desymmetrization
Trost, B. M.; Mino, T. J. Am. Chem. Soc., 2003, 125, 2410.
1,2-Alkynylation of Aldehydes
Trost, B. M.; Weiss, A. H.; von Wangelin, A. J. J. Am. Chem. Soc., 2006, 128, 8.
Tetrametallic Catalysis
Endo, K.; Ogawa, M.; Shibata, T. Angew. Chem., Int. Ed., 2010, 49, 2410.
Bimetallic Salen Complexes (I)
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Keller, F.; Rippert, A. J. Helv. Chim. Acta, 1999, 82, 125.
DiMauro, E. F>; Kozlowski, M. C. Org. Lett., 2001, 3, 1641.
Chen, Z.; Furutachi, M.; Kato, Y.; Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc., 2008, 130, 2170.
Handa, S.; Gnanadesikan, V.; Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc., 2007, 129, 4900.
Bimetallic Salen Complexes (II)
Handa, S.; Nagawa, K.; Sohtome, Y.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed., 2008, 47, 3230.
Bimetallic Catalysis for BINOL Synthesis
Gao, J.; Reibenspies, J. H.; Martell, A. E. Angew. Chem., Int Ed., 2003, 42, 6008.
Bimetallic Hetereogeneous Catalyst
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Nitabaru, T.; Kumagai, N.; Shibasaki, M. Tetrahedron Lett., 2008, 49, 272.
Nitabaru, T.; Nojiri, A.; Kobayashi, M.; Kumagai, N.; Shibasaki, M. J. Am. Chem. Soc., 2009, 131, 13860.
“Robot-like” Bimetallic Pd Catalyst
Jauntze, S.; Peters, R. Angew. Chem., Int Ed., 2008, 47, 9284.
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Separate Metal Centers
Sawamura, M.; Sudoh, M.; Ito, Y. J. Am. Chem. Soc., 1996, 118, 3309.
Jacobsen Catalyst (I)
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Martìnez, L. E.; Leighton, J. L.; Carsten, D. H.; Jacobsen, E. N. J. Am. Chem. Soc., 1995, 117, 5897.
Jacobsen Catalyst (II)
Tokunaga, M.; Larrow, J. F.; Kakiuchi, F.; Jacobsen, E. N. Science, 1997, 277, 936.
Nielsen, L. P. C.; Stevenson, C. P.; Jacobsen, E. N. J. Am. Chem. Soc., 2004, 126, 1360.
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Jacobsen Catalyst (III)
Sammis, G. M.; Jacobsen, E. N. J. Am. Chem. Soc., 2003, 125, 4442.
Sammis, G. M.; Danjo, H.; Jacobsen, E. N. J. Am. Chem. Soc., 2004, 126, 9928.
Bimetallic Epoxide Fluoridation
Kalow, J. A.; Doyle, A. G. J. Am. Chem. Soc., 2010, 132, 3268.
Kalow, J. A.; Doyle, A. G. J. Am. Chem. Soc., 2011, 133, 16001.
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Bridged Bimetallic Catalysts
Belekon’, Y. N.; et al. J. Am. Chem. Soc., 1999, 121, 3968.
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
CO2 Activation With Bimetallic Complexes
Clegg, W.; Harrington, R. W.; North, M.; Pasquale, R. Chem. Eur. J., 2010, 16, 6828.
North, M.; Quek, S. C. Z.; Pridmore, N. E.; Whitwood, A. C.; Wu, X. ACS Cat., 2015, 5, 3398.
Zr-Epoxide Azidination
Nugent, W. A. J. Am. Chem. Soc., 1992, 114, 2768.
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Tethered Bimetallic Catalysis
The Winner!
Konsler, R. G.; Karl, J.; Jacobsen, E. N. J. Am. Chem. Soc, 1998, 120, 10780.
Al Together
Mazet, C.; Jacobsen, E. N. Angew. Chem., Int. Ed., 2008, 47, 1762.
Resolution/Polymerization
Thomas, R. M.; et al. J. Am. Chem. Soc., 2010, 132, 16520.
Vanadium Oxidation of Naphthol
Guo, Q.-X.; Gong, L.-Z.; et al. J. Am. Chem. Soc., 2007, 129, 13927.
Tethered and Bridged Ti-Salen
Zhang, Z.; Wang, Z.; Zhang, R.; Ding, K. Angew. Chem., Int. Ed., 2010, 49, 6746.
Oligomeric/Polymeric Scaffolds
Breinbauer, R.; Jacobsen, E. N. Angew. Chem., Int. Ed., 2000, 39, 3604.
Annis, D. A.; Jacobsen, E. N. J. Am. Chem. Soc., 1999, 121, 4147.
Rossbach, B. M.; Leopold, K.; Weberskirch, R. Angew. Chem., Int. Ed., 2006, 45, 1309.
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Coordination Tethered/Controlled Catalyst
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.
Hydrogen Bond Tethered Catalysts
Park, J.; Lang, K.; Abboud, K. A.; Hong, S. Chem.-Eur. J., 2011, 17, 2236.
Park, J.; Lang, K.; Abboud, K. A.; Hong, S. J. Am. Chem. Soc., 2008, 130, 16484.
Park, J. Hong, S. Chem. Soc. Rev., 2012, 41, 6931.
Nanocage Embedded Catalysts
Yang, H.; Zhang, L.; Zhong, L.; Yang, Q.; Li, C. Angew. Chem., Int. Ed., 2007, 46, 6861.
Thank you for your attention!
http://debbieohi.com/blather2009/?currentPage=6, Accessed 05/20/2015.
Question 1
Catalyst L1 is effective in asymmetric alkylation of enones in the presence of Cu(II) and Zn(II),
while L2 shows very low reactivity and enantioinduction. Provide two structures that are likely
obtained in equilibrium upon treatment of L2 with Cu(II) and Zn(II) that would explain the poor
selectivity (Hint, think about the solubility).
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Endo, K.; Ogawa, M.; Shibata, T. Angew. Chem., Int. Ed., 2010, 49, 2410.
Question 2
Shibasaki showed that a Cu:Sm complex with tetrahydroxy Salen 1 gave syn products from a nitro
Mannich reaction, while most Henry reactions catalyzed prefer to give anti products. For example,
the same ligand complexed with Pd and La was found to give anti products with good selectivity.
Contrast the transition states to explain this difference in selectivity.
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Cu/Sm/1
Handa, S.; Nagawa, K.; Sohtome, Y.; Matsunaga, S.; Shibasaki, M. Angew. Chem., Int. Ed., 2008, 47, 3230.
Question 3
Ito and coworkers demonstrated that a mixture of Pd(S,S)-(R,R)-TRAP and Rh(S,S)-(R,R)-TRAP
gave good enantioselectivity for the asymmetric allylation of α-cyanoesters. Although the
reaction did not proceed without palladium, in the presence of only Pd(S,S)-(R,R)-TRAP the
reaction gave a comparable yield, albeit with no enantioselectivity. Draw the mechanism of the
reaction without Rh (remember that the Pd intermediate is cationic).
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Sawamura, M.; Sudoh, M.; Ito, Y. J. Am. Chem. Soc., 1996, 118, 3309.