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Michael J. Krische
Presented byLouis-Philippe BeaulieuUniversité de Montréal
April 7th 2009
Catalytic C-C Bond Formation via Capture of Hydrogenation Intermediates
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Michael J. Krische: Biographical Information
Obtained a B.S. degree in chemistry from the University of California at Berkeley under the supervision of Professor Henry Rapoport. He received his Ph.D. in 1996 under the mentorship of Professor Barry Trost and he studied with Jean-Marie Lehn at the Université Louis Pasteur as a post-doctoral fellow.
In 1999, he was appointed Assistant Professor at the University of Texas at Austin. He was Promoted to Full Professor in 2004, and was awarded the Robert A. Welch Chair in 2007.
Selected awards include the Tetrahedron Young Investor Award (2009), Novartis Lectureship Award (2008), Elias J. Corey Award (2007) and Dreyfus Teacher Scholar Award (2003).
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Formation of C-C Bonds via Catalytic Hydrogenation and Transfer Hydrogenation: General concept
Conventional reduction
C-C bondformation
Homolytic activation of H2 to form a high-valent dihydride
Heterolytic activation of H2 to form a low-valent monohydride
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Formation of C-C Bonds via Catalytic Hydrogenation and Transfer Hydrogenation: General concept
Ngai, M. Y.; Kong, J. R.; Krische, M. J. J. Org. Chem. 2007, 72, 1063-1072.Skucas, E.; Kong, J. R.; Krische, M. J. J. Am. Chem. Soc. 2007, 129, 7242-7243.
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Tenets of Green Chemistry
Li, C. J.; Trost, B. M. Proc. Natl. Acad. Sci. U. S. A. 2008, 105, 13197-13202.Baran, P. S.; Maimone, T. J.; Richter, J. M. Nature (2007, 446, 404-408.
• Atom economy: Reaction yield = x 100% Quantity of product isolatedTheoretical quantity of product
Atom economy= x 100% MW of desired productMW of all products
• Synthesis without protections
• Development of tandem and cascade reactions
• Use of environmentally bening solvents
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Historical and Industrial Perspective of Catalytic Hydrogenation
Milestones in catalytic hydrogenataion
1500s Paracelsus (1493–1541) and Robert Boyle (1671)
1783 Antoine Lavoisier
1897 Paul Sabatier
1905 Fritz Haber and Carl Bosch
1923 Franz J.E. Fischer and Hans Tropsch
1938 Otto Roelen
1964 Geoffrey Wilkinson
1968-1980
William S. Knowles, Henri B. Kagan, Ryoji Noyori6
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Hydrogen-Mediated Reductive Aldol Coupling
Catalyst Ligand Additive (mol %)
Yield aldol (syn/anti)
Yield 1,4-reduction
Rh(PPh3)3Cl - - 1 % (99:1) 95%
Rh(COD)2OTf
Ph3P - 21% (99:1) 25%
Rh(COD)2OTf
Ph3P KOAc (30) 59% (58:1) 21%
Rh(COD)2OTf
(p-F3CC6H4)3P
- 57% (14:1) 22%
Rh(COD)2OTf
(p-F3CC6H4)3P
KOAc (30) 89% (10:1) 0.1%
Jang, H. Y.; Huddleston, R. R.; Krische, M. J. J. Am. Chem. Soc. 2002, 124, 15156-15157.
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Stereochemical model
(Z)-enolate, Zimmerman-Traxler-type transition state
Stereospecific Z(O)-enolate formation
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Hydrogen-Mediated Reductive Aldol Coupling
Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc. 1976, 98, 2134-2143.
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Hydrogen-Mediated Reductive Aldol Coupling
Entry Ligand [DCM], M Yield (%) dr
1 Ph3P
0.1
31 3:1
2 Ph3As 17 7:1
3 (2-Fur)Ph2P 24 6:1
4 (2-Fur)
2PhP52 15:1
5 (2-Fur) 3P 74 19:1
6a (2-Fur) 3P 0.3 91 16:1a 10 mol% of Li2CO3
Jung, C. K.; Garner, S. A.; Krische, M. J. Org. Lett. 2006, 8, 519-522.
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Hydrogen-Mediated Reductive Aldol Coupling
Jung, C. K.; Garner, S. A.; Krische, M. J. Org. Lett. 2006, 8, 519-522.Ngai, M. Y.; Kong, J. R.; Krische, M. J. J. Org. Chem. 2007, 72, 1063-1072.
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Hydrogen-Mediated Reductive Aldol Coupling: Enantioselective Version
Front view of [Rh(cod)(L)2]OTfomitting the methyl groups, triflate ion, and COD
Entry R1 R2 Yield (%)
syn:anti ee (syn)
1 Me BnO 85 25:1 91
2 Me PhtN 88 50:1 96
3 Me 1-Me-indol-3-yl
92 15:1 86
4 Me Ph 70 25:1 89
5 Et BnO 96 21:1 88
6 Et PhtN 94 45:1 95
7 Et 1-Me-indol-3-yl
97 25:1 90
8 Et Ph 76 22:1 90Bee, C.; Soo, B. H.; Hassan, A.; Iida, H.; Krische, M. J. J. Am. Chem. Soc. 2008, 130, 2746-2747.
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Hydrogen-Mediated Reductive Aldol Coupling
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Ngai, M. Y.; Kong, J. R.; Krische, M. J. J. Org. Chem. 2007, 72, 1063-1072.
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Huddleston, R. R.; Krische, M. J. Org. Lett. 2003, 5, 1143-1146.
Hydrogen-Mediated Reductive Aldol Coupling
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Marriner, G. A.; Garner, S. A.; Jang, H. Y.; Krische, M. J. J. Org. Chem. 2004, 69, 1380-1382.
Hydrogen-Mediated Reductive Aldol Coupling
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Hydrogen-Mediated Conjugated Alkyne-Carbonyl Coupling
Komanduri, V.; Krische, M. J. J. Am. Chem. Soc. 2006, 128, 16448-16449.15
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Hydrogen-Mediated Conjugated Alkyne-Carbonyl Coupling
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Jang, H. Y.; Krische, M. J. Acc. Chem. Res. 2004, 37, 653-661.
Dewar-Chatt-Duncanson Model
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Komanduri, V.; Krische, M. J. J. Am. Chem. Soc. 2006, 128, 16448-16449.
Hydrogen-Mediated Conjugated Alkyne-Carbonyl Coupling
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Komanduri, V.; Krische, M. J. J. Am. Chem. Soc. 2006, 128, 16448-16449.Iida, H.; Krische, M. J. Top. Curr. Chem. 2007; 279, 77-104.
Hydrogen-Mediated Conjugated Alkyne-Carbonyl Coupling
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Kong, J. R.; Cho, C. W.; Krische, M. J. J. Am. Chem. Soc. 2005, 127, 11269-11276.
Hydrogen-Mediated Conjugated Alkyne-Ethyl (N-Sulfinyl)iminoacetates Coupling
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Kong, J. R.; Cho, C. W.; Krische, M. J. J. Am. Chem. Soc. 2005, 127, 11269-11276.20
Hydrogen-Mediated Conjugated Alkyne-Ethyl (N-Sulfinyl)iminoacetates Coupling
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Huddleston, R. R.; Jang, H. Y.; Krische, M. J. J. Am. Chem. Soc. 2003, 125, 11488-11489.
Hydrogen-Mediated Conjugated Alkyne-Carbonyl Coupling
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Hydrogen-Mediated Conjugated Alkyne-Carbonyl Coupling
Jang, H. Y.; Krische, M. J. Acc. Chem. Res. 2004, 37, 653-661.
Competition experiments reveal coupling to the strongest π-acid
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Jang, H. Y.; Hughes, F. W.; Gong, H.; Zhang, J.; Brodbelt, J. S.; Krische, M. J. J. Am. Chem. Soc. 2005, 127, 6174-6175.
Reductive Cyclization of 1,6-Enynesvia Rhodium-Catalyzed Asymmetric Hydrogenation:C−C Bond Formation Precedes Hydrogen Activation
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Reductive Cyclization of 1,6-Enynesvia Rhodium-Catalyzed Asymmetric Hydrogenation:C−C Bond Formation Precedes Hydrogen Activation
Jang, H. Y.; Hughes, F. W.; Gong, H.; Zhang, J.; Brodbelt, J. S.; Krische, M. J. J. Am. Chem. Soc. 2005, 127, 6174-6175.2
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Jang, H. Y.; Hughes, F. W.; Gong, H.; Zhang, J.; Brodbelt, J. S.; Krische, M. J. J. Am. Chem. Soc. 2005, 127, 6174-6175.
Reductive Cyclization of 1,6-Enynesvia Rhodium-Catalyzed Asymmetric Hydrogenation:C−C Bond Formation Precedes Hydrogen Activation
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Reductive Cyclization of Acetylenic Aldehydes
Rhee, J. U.; Krische, M. J. J. Am. Chem. Soc. 2006, 128, 10674-10675.26
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Carbonyl and Imine Z-Dienylation via Multicomponent ReductiveCoupling of Acetylene to Aldehydes and α-Ketoesters
Kong, J. R.; Krische, M. J. J. Am. Chem. Soc. 2006, 128, 16040-16041. Iida, H.; Krische, M. J. Top. Curr. Chem. 2007; 279, 77-104.2
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Carbonyl and Imine Z-Dienylation via Multicomponent ReductiveCoupling of Acetylene to Aldehydes and N-Arylsulfonyl Imines
Kong, J. R.; Krische, M. J. J. Am. Chem. Soc. 2006, 128, 16040-16041.Skucas, E.; Kong, J. R.; Krische, M. J. J. Am. Chem. Soc. 2007, 129, 7242-7243.2
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Reductive Coupling of Disubstituted Alkynes to Activated Ketones
π-Backbonding in the metal-alkyne complex, as described by the Dewar-Chatt-Duncanson model, may facilitate alkyne-C=X (X = O, NR) oxidative coupling by conferring nucleophilic character to the bound alkyne.
Due to relativistic effects, iridium is a stronger π-donor than rhodium: (Ph3P)2M(Cl)(CO), M = Ir, νco = 1965 cm-1; M = Rh, νco = 1980 cm-1.
This may account for the ability of iridium-based catalysts to activate nonconjugated alkynes, which embody higher lying LUMOs.
Ngai, M. Y.; Barchuk, A.; Krische, M. J. J. Am. Chem. Soc. 2007, 129, 280-281..Vaska, L.; Peone, J. Chem. Commun. 1971, 419.2
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Reductive Coupling of Disubstituted Alkynes to Activated Ketones
Ngai, M. Y.; Barchuk, A.; Krische, M. J. J. Am. Chem. Soc. 2007, 129, 280-281..30
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Reductive Coupling of Disubstituted Alkynes to N-Arylsulfonyl Imines
Ngai, M. Y.; Barchuk, A.; Krische, M. J. J. Am. Chem. Soc. 2007, 129, 12644-12645.
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Reverse Prenylation via Iridium-Catalyzed Hydrogenative Coupling of Dimethylallene
Skucas, E.; Bower, J. F.; Krische, M. J. J. Am. Chem. Soc. 2007, 129, 12678-12679.
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Reverse Prenylation via Iridium-Catalyzed Hydrogen Autotransfer and Transfer Hydrogenation
Bower, J. F.; Skucas, E.; Patman, R. L.; Krische, M. J. J. Am. Chem. Soc. 2007, 129, 15134-15135.33
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Reverse Prenylation via Iridium-Catalyzed Hydrogen Autotransfer and Transfer Hydrogenation
Bower, J. F.; Skucas, E.; Patman, R. L.; Krische, M. J. J. Am. Chem. Soc. 2007, 129, 15134-15135.
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A rapid redox equilibration in advance of C-C coupling is operative
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Ruthenium-Catalyzed C-C Bond-Forming TransferHydrogenation
Shibahara, F.; Bower, J. F.; Krische, M. J. J. Am. Chem. Soc. 2008, 130, 6338-6339.Shibahara, F.; Bower, J. F.; Krische, M. J. J. Am. Chem. Soc. 2008, 130, 14120-14122.3
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Ruthenium-Catalyzed C-C Bond-Forming TransferHydrogenation
Shibahara, F.; Bower, J. F.; Krische, M. J. J. Am. Chem. Soc. 2008, 130, 6338-6339.Shibahara, F.; Bower, J. F.; Krische, M. J. J. Am. Chem. Soc. 2008, 130, 14120-14122.
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Enantioselective Iridium-Catalyzed Carbonyl Allylation
Kim, I. S.; Ngai, M. Y.; Krische, M. J. J. Am. Chem. Soc. 2008, 130, 14891-14899.
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Enantioselective Iridium-Catalyzed Carbonyl Allylation
Kim, I. S.; Ngai, M. Y.; Krische, M. J. J. Am. Chem. Soc. 2008, 130, 14891-14899.
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Enantioselective Iridium-Catalyzed Carbonyl Allylation
Kim, I. S.; Ngai, M. Y.; Krische, M. J. J. Am. Chem. Soc. 2008, 130, 14891-14899.
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Enantioselective Iridium-Catalyzed Carbonyl Allylation
Kim, I. S.; Ngai, M. Y.; Krische, M. J. J. Am. Chem. Soc. 2008, 130, 14891-14899.
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Conclusion
• The work of M. J. Krische is the first systematic investigation of the use of catalytic hydrogenation as a method of C-C coupling since the advent of alkene hydroformylation and the Fischer-Tropsch reaction.
•C-C Bond-forming hydrogenation reactions are analogous to conventional carabanion chemistry, yet they feature complete atom-economy . This makes them particularly suitable candidate reactions for industrial-scale applications .
• Several other retrosynthetic disconnections remain to be explored and may lead to other interesting reactions.
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