Transition Metal-catalyzed Cross-coupling Reactions of 过渡金属催化的交叉偶联反应
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accelerate
Kumada-type: Dramatic Enhancement by Additive
Kochi, J. et al. Synthesis 1971, 303
Cahiez, G. et al. Tetrahedron. 2000, 56, 2733
Alkyl Chlorides as Electrophiles: First Example
Kambe, N. et al. J. Am. Chem. Soc. 2002, 124, 4222
Kambe, N. et al. Chem. Lett. 2003, 32, 890
Reaction Mechanism and Evidences
Kambe, N. et al. J. Am. Chem. Soc. 2002, 124, 4222 Kambe, N. et al. Angew. Chem. Int. Ed. 2003, 42, 3412 Kambe, N. et al. Angew. Chem. Int. Ed. 2004, 43, 6180
Boronic Acids as Coupling Partners
Fu, G.C. et al. J. Am. Chem. Soc. 2002, 124, 13662
How do Phosphine Ligands Effect?
Fu, G.C. et al. Angew. Chem. Int. Ed. 2003, 42, 5749
Water is necessary: 1. Non-hydrate salt gave no reaction. 2. Non-hydrate salt + water gave
comparable yields
Fu, G.C. et al. J. Am. Chem. Soc. 2001, 123, 10099
Outline
• Introduction
General reaction pattern and mechanism Difficulties for unactivated alkyl substrates
• Several Reaction Types
Kumada type (RMgX by Mn/Cu/Ni/Pd) Suzuki type (RBR’2 by Pd/Ni ) Negishi type (RZnX / R2Zn by Ni/Pd)
• Conclusion • Outlook
General Reaction Pattern and Mechanism
Activated alkyl electrophiles:
Difficulties of Unactivated Alkyl Substrates
M’ = Pd
accelerate
Alkyl Chlorides and Sulfonates as Electrophiles
Fu, G.C. et al. Angew. Chem. Int. Ed. 2002, 41, 1945 Fu, G.C. et al. Angew. Chem. Int. Ed. 2002, 41, 3910
Alkyl Fluorides as Electrophiles
Kambe, N. et al. J. Am. Chem. Soc. 2002, 125, 5646 Kambe, N. et al. Angew. Chem. Int. Ed. 2007, 46, 2086
Difference in Chemoselectivity
Replace Diorganozinc by Organozinc Halide
Knochel, P. et al. Angew. Chem. Int. Ed. 1998, 37, 2387 Knochel, P. et al. J. Org. Chem. 2002, 67, 79
Pd-Catalyzed Coupling
Sec-Alkyl Electrophiles
Fu, G.C. et al. J. Am. Chem. Soc. 2007, 129, 9602
Brief Summary of Suzuki-type Cross-coupling
Negishi-type: Styrene Additive
Knochel, P. et al. Angew. Chem. Int. Ed. 199ห้องสมุดไป่ตู้, 34, 2723 Knochel, P. et al. Angew. Chem. Int. Ed. 1998, 37, 2387
Chai, C. L. L. et al. Adv. Synth. Catal. 2007, 349, 1015
Brief Summary of Kumada-type Cross-coupling
Suzuki-type: Phosphine did Make Differences
Suzuki, A. etc. Chem. Lett. 1992, 691
Fu, G. C. et al. J. Am. Chem. Soc. 2003, 125, 12527
Pd-NHC Catalyst
Kambe, N. et al. Angew. Chem. Int. Ed. 2007, 46, 2086
Kinetic Study and Proposed Mechanism
Kambe, N. et al. Angew. Chem. Int. Ed. 2007, 46, 2086
Fe Catalyst: Sec-alkyl Electrophiles
Catalytic Cross-coupling Reactions with Unactivated Alkyl Electrophiles
and Alkyl Nucleophiles
Heng Su 04/11/2008 Department of Chemistry Brandeis University