Catalytic Cross-coupling Reactions with Unactivated Alkyl Electrophiles and Alkyl Nucleophiles Heng Su 04/11/2008 Department of Chemistry Brandeis University.

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Presentation transcript:

Catalytic Cross-coupling Reactions with Unactivated Alkyl Electrophiles and Alkyl Nucleophiles Heng Su 04/11/2008 Department of Chemistry Brandeis University

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 / R 2 Zn by Ni/Pd) Conclusion Outlook

General Reaction Pattern and Mechanism Activated alkyl electrophiles:

Difficulties of Unactivated Alkyl Substrates M’ = Pd accelerate

Kumada-type: Dramatic Enhancement by Additive Cahiez, G. et al. Tetrahedron. 2000, 56, 2733 Kochi, J. et al. Synthesis 1971, 303

Alkyl Chlorides as Electrophiles: First Example Kambe, N. et al. Chem. Lett. 2003, 32, 890 Kambe, N. et al. J. Am. Chem. Soc. 2002, 124, 4222

Reaction Mechanism and Evidences Kambe, N. et al. Angew. Chem. Int. Ed. 2004, 43, 6180 Kambe, N. et al. J. Am. Chem. Soc. 2002, 124, 4222 Kambe, N. et al. Angew. Chem. Int. Ed. 2003, 42, 3412

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 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 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 Fu, G.C. et al. J. Am. Chem. Soc. 2001, 123, Water is necessary: 1.Non-hydrate salt gave no reaction. 2.Non-hydrate salt + water gave comparable yields Suzuki, A. etc. Chem. Lett. 1992, 691

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

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

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. 1995, 34, 2723 Knochel, P. et al. Angew. Chem. Int. Ed. 1998, 37, 2387

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 Fu, G. C. et al. J. Am. Chem. Soc. 2003, 125, 12527

Pd-NHC Catalyst Organ, M. G. etc. Org. Lett. 2005, 7, 3805 Organ, M. G. et al. Chem. Eur. J. 2006, 12, 4749

Sec-Alkyl Halides as Electrophiles Fu, G. C. et al. J. Am. Chem. Soc. 2003, 125, 14726

Enantioselective Negishi Cross-coupling Fu, G.C. et al. J. Am. Chem. Soc. 2008, 130, 2756 R 1 = n-Bu, regioselectivity = 1.9:1 = others, >20:1 Fu, G.C. et al. J. Am. Chem. Soc. 2005, 127, 4594 Fu, G.C. et al. J. Am. Chem. Soc. 2005, 127, 10482

Radical or Nonradical Pathway? Vicic, D. A. et al. J. Am. Chem. Soc. 2006, 128, Only C 2 H 6 and C 2 D 6 was observed

Formal Synthesis of Fluvircinine A 1 Fu, G.C. et al. J. Am. Chem. Soc. 2008, 130, 2756

Formal Synthesis of Fluvircinine A 1 : Retrosynthesis Fu, G.C. et al. J. Am. Chem. Soc. 2008, 130, 2756

Brief Summary of Negishi-type Cross-coupling Fu, G.C. et al. J. Am. Chem. Soc. 2008, 130, 2756

Conclusion

Outlook Unactivated tertiary alkyl chlorides as electrophiles Tertiary alkyl boron compounds as nucleophiles Enantioselective cross-coupling of unactivated electrophiles

Acknowledgement