Pd-catalyzed stereospecific allyl-aryl coupling of allylic ...
Metal-Catalyzed Cross-Coupling of Two sp -Carbons ... · Metal-Catalyzed Cross-Coupling of Two...
Transcript of Metal-Catalyzed Cross-Coupling of Two sp -Carbons ... · Metal-Catalyzed Cross-Coupling of Two...
Metal-Catalyzed Cross-Coupling of Two sp3-Carbons: Challenges and Solutions
Alex Predeus January 17, 2007
Problems of Unactivated Alkyl Electrophiles: Pd
• Unactivated alkyl halides (even CH3I) react slowly with Pd0 complexes.
Note: The reaction of CH3I and phosphane-Ni0 complex is about 107 times faster and follows complex pathway in which radical species may be involved.
• β-H-Elimination competes with the usually slower transmetallation.
Note: β-H-Elimination requires vacant coordination sight and and the feasibility of arranging M-C-C-H atoms in the same plane.
• Reductive elimination from σ-alkyl-π-allyl–PdII and di-π-allyl–PdII
is usually slow. Note: In many cases elimination can be accelerated by the
addition of π-acceptors, stabilizing the low-valent state of the metal.
Formation of Alkylmetal Complexes • Substitution (“metathesis”):
ox. state change = 0 • Olefin insertion into metal-ligand bond:
ox. state change = 0 • Radical oxidative addition:
ox. state change = +1 • Carbocation (or its precursor) oxidative addition:
ox. state change = +2
I AuIII
CH3
CH3
PPh3 D3C AuIII
CH3
CH3
PPh3CD3Li
- LiI
L2PtIIH
ClH2C CH2 L2PtII
CH2CH3Cl
+
CH3 CrIIen2+ CrIIIen2+H3C+
D3C AuIIICH3
CH3
PPh3CD3I (CH3)2AuILi+PPh3
Outline: Reactions
1. Early examples
2. Copper-catalyzed reactions
3. Nickel-catalyzed reactions
4. Palladium-catalyzed reactions
5. Other catalysts
Early Examples Including Copper: Cuprates and Kochi Coupling
R2CuLi + R' LG R R'
R MgX + R' LG
R, R' - mostly 1°; LG = RCOO, X, OTs, etc.
Li2CuCl4R R'
~10%
R, R' - mostly 1°; LG = X
Suzuki Coupling: Some Alkyliodides
Ishiyama, T.; Abe, S.; Miyaura, N.; Suzuki, A. Chem. Lett. 1992, 691 - 694
Nickel-Catalyzed Coupling: 2o Organozinc Derivatives
F
4
Jensen, A.E.; Knochel, P. J. Org. Chem. 2002, 67, 79 - 85
Nickel-Catalyzed Coupling: Grignard Reagents, Revised
N. Kambe et. al., JACS 2002, 124, 4222; JACS 2003, 125, 5646
Suzuki Coupling: Alkyl Bromides
Netherton, M.R.; Dai, C.; Neuschutz, K.; Fu, G.C. J. Am. Chem. Soc.
2001, 123, 10099
Suzuki Coupling: Alkyl Chlorides
Kirchhoff, J.H.; Dai, C.; Fu, G.C. Angew. Chem. Int. Ed. Engl.
2002, 41, No. 11, 1945
Manganese-Catalyzed Coupling
Donkervoort, J. G.; Vicario, J. L.; Jastrzebski, J. T. B. H.; Cahiez,G.; van Koten, G. Recl. Trav. Chim. Pays-Bas 1996, 115, 547-548.
Donkervoort, J. G.; Vicario, J. L.; Jastrzebski, J. T. B. H.; Gossage, R. A.; Cahiez, G.; van Koten, G. J. Organomet. Chem. 1998, 558, 61-69.
Cobalt-Phosphine-Catalyzed
Cross-coupling
Reaction
Tsuji, T.; Yorimitsu, H.; Oshima, K. Angew. Chem., Int. Ed. 2002, 41, 4137-4139