1. Carbon-Carbon Bond Activation: Rhodium-
Catalyzed Reactions of Quinolinyl Ketones
with Michael Acceptors
Christian Otteman
Johnson Group
July 17th, 2015

2. Johnson Group Goals
R R'
O [Rh]
+
R" R
O
R"
A EB C D
[M]

3. Carbon-Carbon Bond Activation
Douglas, et. al. J. Am. Chem. Soc. 2009, 131, 412.
• C-C single bonds are generally unreactive
• Selective activation through use of transition metals

4. Carboacylation Mechanism
Oxidative
addition
Association
Alkene
insertion
Reductive
elimination
Lutz, Rathbun, Stevenson, Boman, Powell, Baxter, Zona, Johnson J. Am. Chem. Soc. 2012, 134, 715

5. Palladium-Catalyzed Reactions
Miura, et. al. J. Am. Chem. Soc. 2001, 123, 10407.
Bour, Green, Winton, Johnson J. Org. Chem. 2013, 78, 1665.

6. Developing New Methods
• Quinolinyl ketone directing group
• Bond selectivity
• Ortho directing groups in phenyl ring
• Ortho substituent effects
• Create new substrate for catalysis

7. Proposed Mechanism
X
β-hydride
elimination
>95%

8. Reactions with Michael Acceptors
(excess)

9. Reaction Scope: Quinolinyl Ketones
• * indicates isolated yield
30%, 17%*>95%, 39%* 33%, 18%* 51%, 26%* 13%, 12%*
>95%, 25%*>95%, 76%* 42%, 42%* 85%, 72%*

10. Reaction Scope: Quinolinyl Ketones
• * indicates isolated yield
85%, 29%*>95%, 26%* 9% 31%, 19%* 95%, 25%*
64%, 38%* 30%, 10%* 41%, 20%* 12%

11. Reaction Scope: Michael Acceptors
• * indicates isolated yield
>95%, 39%* >95%, 26%* 34%, 10%*
67%, 26%* >95%

12. Reaction Scope: Michael Acceptors
• * indicates isolated yield
>95%, 76%* 64%, 38%*
95%, 45%*
55%, 31%* 92%30%, 10%*
65% 40%, 16%*
>95%, 25%*
50%, 26%*

13. Conclusions
• Reaction proceeds catalytically
• Isolations successful for many reactions
• Characterizations complete for several products
• Reaction runs based on directing groups and sterics
39%* 18%* 76%*
• * indicates isolated yield

14. Future Work
• Improve current isolation results
• Size exclusion chromatography
• Continue to broaden reaction scope
• Examine new directing groups
• Moving past quinolinyl ketones

15. Acknowledgements
• Johnson group lab members
• Caroline Gregerson, Kathryn Trentadue,
Erik Phipps, Janelle Kirsch
• NSF
• Hope College