Hydrogen-Mediated C-C Bond Formation€¦ · Hydrogen-Mediated C-C Bond Formation ... industrial...
Transcript of Hydrogen-Mediated C-C Bond Formation€¦ · Hydrogen-Mediated C-C Bond Formation ... industrial...
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EPFL - ISIC - LSPN
LSPN Group Seminar
Mathias Mamboury February 18, 2016
Hydrogen-Mediated C-C Bond Formation
History and selected examples
The Research of Prof. Michael Krische (University of Texas at Austin)
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Table of contents
1) Introduction
2) Homogeneous catalytic hydrogenation
History and hydroformylation
3) Rhodium catalysis
Aldol couplings
4) Iridium catalysis
Allylation / crotylation
5) Ruthenium catalysis
Crotylation & hydroacylation
6) Conclusion
2 Mathias Mamboury February 18, 2016 LSPN Group Seminar
H2
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1) Introduction
2) Homogeneous catalytic hydrogenation
3) Rhodium catalysis
4) Iridium catalysis
5) Ruthenium catalysis
6) Conclusion
3
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1) Introduction
From the 1st homogeneous catalytic hydrogenation by Calvin in 1938…
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Science 2012, 336, 324-327
J. Am. Chem. Soc. 2011, 133, 12795-12800
… to highly atom economical transformations of great interest :
Trans. Faraday Soc. 1938, 34, 1181-1191
Without H2 !
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1) Introduction
Professor Michael J. Krische :
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• 1986-1989 : B.S. Chemistry / University of California at Berkeley / Prof. H. Rapoport
• 1990-1996 : Ph.D. Chemistry / Stanford University / Prof. B. M. Trost
• 1997-1999 : NIH Post-Doc. / Université Louis Pasteur / Prof. J.-M. Lehn
• Since 1999 : Professor at the University of Texas at Austin
2002
2016
→ 1st H2-mediated C-C coupling
> 90 papers published in this field
Early years : Rhodium Currently : Iridium & Ruthenium
Krische Ir-Catalyst
Commercially available: AldrichCPR : 92 CHF / 100 mg
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1) Introduction
2) Homogeneous catalytic hydrogenation
3) Rhodium catalysis
4) Iridium catalysis
5) Ruthenium catalysis
6) Conclusion
6
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• 1938, Calvin : 1st homogeneous catalytic hydrogenation
• 1961, Halpern : 1st hydrogenation of activated alkenes
• 1966, Wilkinson : 1st hydrogenation of unactivated alkenes and alkynes
2) Homogeneous catalytic hydrogenation
The History of homogeneous catalytic hydrogenation :
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Trans. Faraday Soc. 1938, 34, 1181-1191
J. Am. Chem. Soc. 1981, 63, 753-754
J. Chem. Soc. A 1966, 1711-1732
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• 1971, Kagan : 1st enantioselective hydrogenation of alkenes
• 1977, Crabtree : highly efficient Ir-catalyst for the hydrogenation of alkenes
• 1987, Noyori : Ru-catalyst for the hydrogenation of alkenes
2) Homogeneous catalytic hydrogenation
The History of homogeneous catalytic hydrogenation :
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J. Chem. Soc. D 1971, 481
J. Organomet. Chem. 1977, 135, 395-403
J. Org. Chem. 1987, 52, 3174-3176
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• Ater 2000 :
• Late 1960 : homogeneous transfer hydrogenation
• 1995, Noyori : 1st efficient enantioselective hydrogenation of aromatic ketones
2) Homogeneous catalytic hydrogenation
The History of homogeneous catalytic hydrogenation :
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J. Am. Chem. Soc. 1995, 117, 2675-2676
Chem. Rev. 1974, 74, 567-580 (refs 9-13)
Early transition metals.
Chemo-, diastereo- and enantioselectivity.
Ability to reduce almost any unsaturated functional group.
Applications for energy and environment ?
etc.
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2) Homogeneous catalytic hydrogenation
An intruiging and inspiring reaction left aside :
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• 1938, Roelen : Hydroformylation
« Hydroformylation is one of the most important industrial processes based on homogeneous catalysis ».
DE Patent 849 548 (1938)
C-C bond formation with H2 as terminal reductant !
Acc. Chem. Res. 2003, 36, 264–275
Powerfull concept : - Atom economic - Versatile if applicable with… … any carbonyl group other than CO … any alkene or alkyne
Another point of view :
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1) Introduction
2) Homogeneous catalytic hydrogenation
3) Rhodium catalysis
4) Iridium catalysis
5) Ruthenium catalysis
6) Conclusion
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3) Rhodium-catalysis
How could we form a C-C bond ?
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Strategy :
Trap a carbonyl compound with one of the intermediates (or similar).
Challenge :
Generate a Rh-intermediate that is nucleophilic enough to
attack the carbonyl. Proposal :
Rh-enolate !
Hydrogenation with the Wilkinson catalyst :
J. Chem. Soc. A 1968, 2665-2671
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3) Rhodium-catalysis
1st (almost) H2-mediated C-C coupling beyond hydroformylation : aldol coupling
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J. Am. Chem. Soc. 2002, 124, 15156-15157 Org. Lett. 2003, 5, 1143-1146 Org. Lett. 2004, 6, 691-694 Acc. Chem. Res. 2004, 37, 653-661
Postulated intermediate :
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3) Rhodium-catalysis
Observation during the optimization :
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Org. Lett. 2003, 5, 1143-1146 Acc. Chem. Res. 2004, 37, 653-661
Mechanism :
Neutral Rh(I) → homolytic cleavage of H2 → 1,4-reduction Cationic Rh(I) + base → heterolytic cleavage of H2 → traping
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3) Rhodium-catalysis
Intermolecular aldol coupling and diastereoselectivity :
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Org. Lett. 2006, 8, 519-522 Org. Lett. 2006, 8, 5657-5660
Ligand Yield d.r.
PPh3 31% 3:1
(2-furyl)Ph2P 24% 6:1
(2-furyl)2PhP 52% 15:1
(2-furyl)3P 74% 19:1
(2-furyl)3P =
Simplest explanation, among others :
The rhodium center is more Lewis acidic, rendering the Zimmermann-Traxler transition state more «tight» :
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3) Rhodium-catalysis
Enantioselective aldol coupling (2008) :
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J. Am. Chem. Soc. 2008, 130, 2746-2747
Scope : Design of the ligand :
Etc.
Limitations :
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3) Rhodium-catalysis
Summary :
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Rh-catalyzed aldol couplings are the first H2-mediated C-C couplings beyond hydroformylation :
• Atom economic • Mild conditions • Intra- and intermolecular • High diastereoselectivities • Enantioselective for MVK
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3) Rhodium-catalysis
Other transformations with rhodium :
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J. Am. Chem. Soc. 2005, 127, 11269-11276 Org. Lett. 2006, 8, 3873-3876 Org. Lett. 2007, 89, 3745-3748
Postulated intermediates :
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3) Rhodium-catalysis
From rhodium to iridium :
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*J. Am. Chem. Soc. 2007, 129, 8432-8433 (note 9) J. Am. Chem. Soc. 2007, 129, 12644-12645 J. Am. Chem. Soc. 2007, 129, 280-281
Major limitation : only works with conjugated alkynes
Alternative :
• Stronger π-donor than Rh (relativistic effects) • May react with higher lying non-conjugated LUMOs • π-backbonding to alkyne may render the Ir-alkyne intermediate more nucleophilic*
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1) Introduction
2) Homogeneous catalytic hydrogenation
3) Rhodium catalysis
4) Iridium catalysis
5) Ruthenium catalysis
6) Conclusion
20
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4) Iridium-catalysis
Enantioselective carbonyl allylation :
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J. Am. Chem. Soc. 2008, 130, 6340-6341 J. Am. Chem. Soc. 2008, 130, 14891-14899
→ Transfer hydrogenation (= TH) with i-PrOH as hydrogen donor !
One step further :
→ Hydrogen auto-transfer !
Only byproducts: • Acetone • Acetic acid
Only byproduct: • Acetic acid
Highly atom economic !
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4) Iridium-catalysis
Enantioselective carbonyl allylation :
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J. Am. Chem. Soc. 2008, 130, 6340-6341 J. Am. Chem. Soc. 2008, 130, 14891-14899
Benzoic acid Yield
o-NO2BzOH 39%
m-NO2BzOH 81%
p-NO2BzOH 49
Optimization : •
•
Scope :
Etc.
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4) Iridium-catalysis
Enantioselective carbonyl allylation :
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J. Am. Chem. Soc. 2008, 130, 14891-14899 J. Am. Chem. Soc. 2009, 131, 2514-2520
Mechanism :
This pre-formed catalyst shows higher performance (% and e.e.) than the in-situ prepared catalyst !
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4) Iridium-catalysis
Related reactions : crotylation & alkoxyallylation
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Crotylation :
J. Am. Chem. Soc. 2009, 131, 2514-2520 J. Am. Chem. Soc. 2010, 132, 1760-1761
Krische Ir-Catalyst
Commercially available: AldrichCPR : 92 CHF / 100 mg
Alkoxyallylation :
Chem. Commun. 2011, 47, 10028-10030
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4) Iridium-catalysis
Addition to diols :
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J. Am. Chem. Soc. 2010, 132, 1760-1761
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4) Iridium-catalysis
Summary :
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Ir-catalyzed allylations (and similar transformations) are among the first TH-mediated C-C couplings :
• Atom economic • No H2 gas • Simple conditions • Diastereo- and enantioselectivity • Bypasses redox manipulations
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1) Introduction
2) Homogeneous catalytic hydrogenation
3) Rhodium catalysis
4) Iridium catalysis
5) Ruthenium catalysis
6) Conclusion
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5) Ruthenium-catalysis
Crotylation : 1st C-C bond formation with ruthenium under TH
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J. Am. Chem. Soc. 2008, 130, 6338-6339 J. Am. Chem. Soc. 2008, 130, 14120-14122
→ All attempts using iridium failed for non-cyclic dienes !
Observation: → Suppressed by addition of a ligand to block the coordination sites required for β–hydride elimination.
Hydroacylation :
→ No additionnal ligand !
Fully atom economic !
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5) Ruthenium-catalysis
Crotylation and hydroacylation :
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J. Am. Chem. Soc. 2008, 130, 6338-6339 J. Am. Chem. Soc. 2008, 130, 14120-14122
These 2 reactions also work with
→ All oxidation levels of substrate and product are accessible !
→ No redox manipulations of starting materials et products required !
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5) Ruthenium-catalysis
Enantioselective crotylation :
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Science 2012, 336, 324-327 J. Am. Chem. Soc. 2012, 134, 20628-20631
Inversion of diastereoselectivity :
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5) Ruthenium-catalysis
Enantioselective crotylation :
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Science 2012, 336, 324-327
Mechanism :
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5) Ruthenium-catalysis
Summary :
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Ru-catalyzed crotylations are among the first TH-mediated C-C couplings :
• Fullly atom economic • Bypasses redox manipulations • No H2 gas • Simple conditions • Diastereo- and enantioselectivity
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1) Introduction
2) Homogeneous catalytic hydrogenation
3) Rhodium catalysis
4) Iridium catalysis
5) Ruthenium catalysis
6) Conclusion
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6) Conclusion
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A long way :
1938 :
Years 2000 :
• Beautifull concepts
• Complementary metals • Modern chemistry :
• Simple and cheap starting materials • Valuable products • Diastereo- and enantioselectivity • Atom economic / green
« Because organic molecules are compounds composed of C and H, the formation of C-C bonds under (transfer) hydrogenation conditions is a natural end point in the evolution of strategies for organic synthesis ».
Science 2012, 336, 324-327
Trans. Faraday Soc. 1938, 34, 1181-1191
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6) Conclusion
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This presentation is not a complete review on H2-mediated C-C bond formation !
See research.cm.utexas.edu/mkrische for the full list of publications !
Thank you for your attention !
Questions / discussions ?