Hydrogen-Mediated C-C Coupling Beyond Hydroformylation: Michael J. Krische
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Formation of C-C Bonds via Catalytic Hydrogenation and Transfer Hydrogenation Professor Michael J. Krische University of Texas at Austin BASF – 150 th Anniversary Celebration Chicago, Illinois; June 22-24, 2015
Transcript of Hydrogen-Mediated C-C Coupling Beyond Hydroformylation: Michael J. Krische
Formation of C-C Bonds via Catalytic
Hydrogenation and Transfer HydrogenationProfessor Michael J. Krische University of Texas at Austin
BASF – 150th Anniversary CelebrationChicago, Illinois; June 22-24, 2015
Victor Grignard, C. R. Acad. Sci. 1900, 130, 1322.
1912
Paul Sabatier, C. R. Acad. Sci. 1896, 1240.
The Haber-Bosch Reaction
N2 + 3 H2 → NH3 100 M Tons/Yr
12% of GMP Reactions are Hydrogenations
Only 3% are Oxidations
Asymmetric H2: > 50% Chiral Compounds Made Industrially
Notwithstanding Biocatalysis/Resolution
OPRD 2005, 9, 253CE&N 9/05, 2005
Victor Grignard, C. R. Acad. Sci. 1900, 130, 1322.
1912
Paul Sabatier, C. R. Acad. Sci. 1896, 1240.
Largest Volume Application of Enantioselective Catalysis (1996, Metolachlor)
Victor Grignard, C. R. Acad. Sci. 1900, 130, 1322.
1912
Paul Sabatier, C. R. Acad. Sci. 1896, 1240.
Victor Grignard, C. R. Acad. Sci. 1900, 130, 1322.
Hydrogen-Mediated Carbonyl Addition
Hydrogenation: > 10% of GMP Reactions
Paul Sabatier, C. R. Acad. Sci. 1896, 1240.
1912
Victor Grignard, C. R. Acad. Sci. 1900, 130, 1322.
1912
Otto Roelen – Hydroformylation, 1938
Hydrogen-Mediated Carbonyl Addition
Hydrogenation: > 10% of GMP Reactions
Reviews: Angew. Chem. Int. Ed. 2009, 48, 34; Top. Organomet. Chem. 2011, 43, 107.
J. Am. Chem. Soc. 2008, 2747
X-Ray Crystal StructureRhL2(cod)
JACS 2008, 2747
X-Ray Crystal StructureRhL2*(cod)
JACS 2008, 2747
JACS 2006, 17051; Org. Lett. 2006, 5657; JACS 2008, 12592.
Oppolzer JACS 1993, 1593; Wipf JOC 1998, 6454
Reactants M.W. = C13H16O
Product M.W. = C13H18O
H2
Ni-Catalyzed Alkyne-Carbonyl Reductive Coupling: Montgomery JACS 1997, 6098; Jamison JACS 2003, 3442.
JACS 2007, 12644.
JACS 2007, 12644.
JACS 2005, 11269.
JACS 2006, 16448.
Angew. Chem. Int. Ed. 2006, 6885
H2
H2
C=O Addition via ReactantREDOX Pairs
C=N Addition via ReactantREDOX Pairs
Metal Price
01/2014-01/2015*Pt Pd Rh Ir Ru
$$ / Ounce 1,381 809 1,175 555 64
$$ / Mole 9,503 3,037 4,265 3,763 228
http://www.platinum.matthey.com
Merck Process Tetrahedron Asymm. 2003, 3581
JACS 2007, 15134; JACS 2011, 1141
ACIE 2015, 5465
JACS 2009, 5054; Org. Lett. 2010, 2514.JACS 2009, 5054; Org. Lett. 2010, 2514.
JACS 2009, 5054; Org. Lett. 2010, 2514.
JACS 2015, 3161
JACS 2015, 3161
2015 – Submitted for Publication
JACS 2015, 1798
JACS 2009, 10366; Nature Chem. 2011, 287; ACIE 2011, 5687; Chem. Sci. 2013, 1876.
Angew. Chem. Int. Ed. 2015, In Press; Submitted for Publication
Angew. Chem. Int. Ed. 2012, 2972
Angew. Chem. Int. Ed. 2012, 7830
Polyketide Natural Products: Commercial Medicines From Soil Bacteria
Polyketide Natural Products: Commercial Medicines From Soil Bacteria
Review: Nat. Prod. Rep. 2014, 31, 504
Review: Nat. Prod. Rep. 2014, 31, 504
Polyketide Natural Products: Commercial Medicines From Soil Bacteria
Redox-Triggered C-C Coupling of Dienes
Classical Crotylation: Brown JACS 1983, 2092
JACS 2008, 6338; JACS 2008, 14120.
JACS 2008, 6338; JACS 2008, 14120.
Redox-Triggered C-C Coupling of Dienes
Science 2012, 336, 324; JACS 2012, 20628.
Science 2012, 336, 324; JACS 2012, 20628.
Science 2012, 336, 324; JACS 2012, 20628.
Science 2012, 336, 324; JACS 2012, 20628.
Science 2012, 336, 324; JACS 2012, 20628; Computation - Houk JACS 2015 In Press.
X-Ray Crystal Structure
Science 2012, 336, 324; JACS 2012, 20628 ; Computation - Houk JACS 2015 In Press.
X-Ray Crystal Structure
Science 2012, 336, 324; JACS 2012, 20628.
Tsuji-Trost Reaction
Redox-Triggered Carbonyl Addition
Hartwig ACIE 2008, 1928
JACS 2008, 6340JACS 2008, 14891.
JACS 2008, 6340JACS 2008, 14891.
JACS 2008, 6340; JACS 2008, 14891. JOC 2011, 2350.
JACS 2008, 6340; JACS 2008, 14891. Org. Lett. 2012, 6302.
JACS 2008, 6340; JACS 2008, 14891. Org. Lett. 2012, 6302.
Angew. Chem. Int. Ed. 2013, 3195; Chem. Eur. J. 2014, 13382.
Recovery and Recycling of Catalyst
1st Run
2nd Run
3rd Run
JACS 2014, 8911
JACS 2014, 8911
JACS 2012, 11100; ACIE 2011, 3493; ACIE 2011, 4173
Review: Angew. Chem. Int. Ed. 2014, 9142
ACIE 2009, 5018; JACS 2010, 15559
The Horeau Principle: Tetrahedron 1973, 1055
ACIE 2009, 5018; JACS 2010, 15559
ACIE 2009, 5018; JACS 2010, 15559
Prior Syntheses (LLS)45 Steps (Mori)31 Steps (Rychnovsky )29 Steps (Evans)
20 Steps (LLS) JACS 2010, 15559
JACS 2011, 12795
JACS 2011, 12795
JACS 2011, 12795
Prior Syntheses35 Steps (Danishefsky)
28 Steps (Cossy)22 Steps (Leighton)
38 Steps (Miyashita)49 Steps (Guindon) JACS 2015, In Press
13 StereocentersNow
13 Steps
Over 18 Total Syntheses (1979-2015)
JACS 2013, 4223
6-Deoxyerythronolide BMasamune (26 Steps)Danishefsky (39 Steps)
Evans (23 Steps), White (23 Steps)JACS 2013, 4223
6-Deoxyerythronolide BMasamune (26 Steps)Danishefsky (39 Steps)
Evans (23 Steps), White (23 Steps)JACS 2013, 4223
Org. Lett. 2006, 891; Org. Lett. 2009, 3108;JACS 2011, 13876; JACS 2014, 9142.
Org. Lett. 2006, 891; Org. Lett. 2009, 3108;JACS 2011, 13876; JACS 2014, 9142.
JACS 2011, 13876; JACS 2014, 9142.
Review - Nat. Prod. Rep. 2014, 504.
Review - Nat. Prod. Rep. 2014, 504.
Victor Grignard, C. R. Acad. Sci. 1900 , 130, 1322.
Paul Sabatier, C. R. Acad. Sci. 1896, 1240.
Hydrogen-Mediated Carbonyl Addition
Reviews - Nat. Prod. Rep. 2014, 504; Angew. Chem. Int. Ed. 2014, 9142
1912
Victor Grignard, C. R. Acad. Sci. 1900 , 130, 1322.
Paul Sabatier, C. R. Acad. Sci. 1896, 1240.
Hydrogen-Mediated Carbonyl Addition
Reviews - Nat. Prod. Rep. 2014, 504; Angew. Chem. Int. Ed. 2014, 9142
1912
February 7, 2015
