Transition-Metal Catalyzed Direct Addition of
Unactivated C-H Bonds to Polar Unsaturated
Bonds
Lei Yang and Hanmin. Chem. Rev. 2015, 115, 3517-3568
AK Seminar
Julio César Orejarena Pacheco
09. Dec. 2015
1
Table of Contents
1. Introduction.
2. Transition
Metal
Catalyzed
Direct
Addition Of C(sp2)-H Bonds To Polar
Unsaturated Bonds Via C-H Activation.
3. Transition
Metal
Catalyzed
Direct
Addition Of C(sp3)-H Bonds To Polar
Unsaturated Bonds Via C-H Activation.
2
1. INTRODUCTION
Overview
C-H activation: Catalytic or stoichiometric reactions of transition metal
complexes with unreactive C-H bonds of alkanes, arenes, or alkyl chains to
form products containing a new metal-carbon bond.
Major challenge:
• selective activation
• catalytic process
The reactions are thermodynamically unfavored in many cases
Labinger, J. A.; Bercaw, J. E. Nature 2002, 417, 507.
3
1.2. Catalytic Cycle
Yang, L.; Huang, H. Chem. Rev. 2015, 115, 3468.
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2. Transition Metal Catalyzed Direct
Addition Of C(sp2)-H Bonds To Polar
Unsaturated Bonds Via C-H Activation.
2.1. Addition of C(sp2)-H to C-C Double
Bonds
5
2.1.1. Addition of Aryl C-H to C-C
Double Bonds
•
No suitable for olefins with polar C-C double bonds.
Oxidative Addition
a. Murai, S.; Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani, A.; Sonoda, M.; Chatani, N. Nature
1993, 529. b. Tan, K. L.; Bergman, R. G.; Ellman, J. A. J. Am. Chem. Soc. 2002, 124, 13964.
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2.1.1. Addition of Aryl C-H to C-C
Double Bonds
Proton-Transfer
Yang, L.; Qian, B.; Huang, H. Chem. Eur. J. 2012, 18, 9511.
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2.1.1. Addition of Aryl C-H to C-C
Double Bonds
base-assisted
proton abstraction
Ryu, J.; Cho, S. H.; Chang, S. Angew. Chem., Int. Ed. 2012, 51, 3677.
8
2.1.1. Addition of Aryl C-H to C-C
Double Bonds
Ryu, J.; Cho, S. H.; Chang, S. Angew. Chem., Int. Ed. 2012, 51, 3677.
9
2.1.1. Addition of Aryl C-H to C-C
Double Bonds
Shi, Z.; Grohmann, C.; Glorius, F. Angew. Chem., Int. Ed. 2013, 52, 5393.
10
2.1.2. Addition of olefinic C-H to C-C
Double Bonds
Rh(III)/Rh(I)
a. Kakiuchi, F.; Tanaka, Y.; Sato, T.; Chatani, N.; Murai, S. Chem. Lett. 1995, 679. b. Neely, J.
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M.; Rovis, T. J. Am. Chem. Soc. 2013, 135, 66.
2.1.2. Addition of olefinic C-H to C-C
Double Bonds
Liu, P.; Wang, H.-S.; Pan, Y.-M.; Dai, W.-L.; Liang, H.; Chen, Z.-F. Chem. Commun. 2013, 49,
12
5295.
2.1.3. Addition of Aldehydic C-H to C-C
Double Bonds
Oxidative Addition
Barnhart, R. W.; Wang, X.; Noheda, P.; Bergens, S. H.; Whelan, J.; Bosnich, B. J. Am. Chem.
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Soc. 1994, 116, 1821.
2.1.3. Addition of Aldehydic C-H to C-C
Double Bonds
Osborne, J. D.; Willis, M. C. Chem. Commun. 2008, 5025.
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2.1.3. Addition of Aldehydic C-H to C-C
Double Bonds
Jo, E.-A.; Jun, C.-H. Eur. J. Org. Chem. 2006, 2504.
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2.2. Addition of C(sp2)-H to C-C Triple
Bonds
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2.2.1 Addition of Aryl C-H to C-C Triple
Bonds
s-Aryl-Pd
Complexes
Jia, C.; Lu, W.; Oyamada, J.; Kitamura, T.; Matsuda, K.; Irie, M.; Fujiwara, Y. J. Am. Chem. Soc.
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2000, 122, 7252.
2.3. Addition of C(sp2)-H to C-O Double
bonds
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2.3.1. Addition of Aryl C-H to Aldehydes
and Ketones
Proton-Transfer
Lian, Y.; Bergman, R. G.; Lavis, L. D.; Ellman, J. A. J. Am. Chem. Soc. 2013, 135, 7122.
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2.3.1. Addition of Aryl C-H to Aldehydes
and Ketones
Oxidative addition or
electrophilic metallation
mechanism
a. Tsuchikama, K.; Hashimoto, Y.; Endo, K.; Shibata, T. Adv. Synth. Catal. 2009, 351, 2850.20b.
Shibata, T.; Hashimoto, Y.; Otsuka, M.; Tsuchikama, K.; Endo, K. Synlett 2011, 14, 2075.
2.3.2. Addition of Aldehydic C-H to
Aldehydes and Ketones
Oxidative addition
one rhodium catalyst acts as a Lewis acid by
coordinating the oxygen atom of the aldehyde and
a second rhodium catalyst participates in the
oxidative addition
Kou, K. G. M.; Le, D. N.; Dong, V. M. J. Am. Chem. Soc. 2014, 136, 9471.
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2.4. Addition of C(sp2)-H to C-N Double
bonds
22
2.4.1. Addition to Imines
Oxidative addition
Gao, K.; Yoshikai, N. Chem. Commun. 2012, 48, 4305.
23
2.4.1. Addition to Imines
Proton-Transfer
Lian, Y.; Huber, T.; Hesp, K. D.; Bergman, R. G.; Ellman, J. A. Angew. Chem., Int. Ed. 2013,2452,
629.
2.5. Addition of C(sp2)-H to C-N Triple
Bonds
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s-Aryl-Pd
Complexes
Jiang, T.-S; Wang, G.-W. Org. Lett. 2013, 15, 788.
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2.6. Addition of C(sp2)-H to Carbon
Monoxide
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Pd(0)/Pd(II)
Rajeshkumar, V.; Lee, T.-H.; Chuang, S.-C. Org. Lett. 2013, 15, 1468.
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3. Transition Metal Catalyzed Direct
Addition Of C(sp3)-H Bonds To Polar
Unsaturated Bonds Via C-H Activation.
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3.1. Addition of C(sp3)-H to C-C Double
Bonds
Komai, H.; Yoshino, T.; Matsunaga, S.; Kanai, M. Org. Lett. 2011, 13, 1706.
30
3.1. Addition of C(sp3)-H to C-C Double
Bonds
Lahm, G.; Opatz, T. Org. Lett. 2014, 16, 4201
31
3.2. Addition of C(sp3)-H to C-O Double
Bonds
Graves, V. B.; Shaikh, A. Tetrahedron. Lett. 2013, 54, 695
32
3.3. Addition of C(sp3)-H to C-N Double
Bonds
Rueping, M.; Tolstoluzhsky, N. Org. Lett. 2011, 13, 1095.
33
3.4. Addition of C(sp3)-H to Carbon
Monoxide
McNally, A.; Haffemayer, B.; Collins, B. S. L.; Gaunt, M. J. Nature 2014, 510, 129.
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3.4. Addition of C(sp3)-H to Carbon
Monoxide
Xie, P.; Xia, C.; Huang, H. Org. Lett. 2013, 15, 3370.
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Vielen Dank für die Aufmerksamkeit
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