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Iron Catalyzed Cross-Coupling Reaction: Recent Advances and Primary Mechanism

Iron Catalyzed Cross-Coupling Reaction: Recent Advances and Primary Mechanism. Wang Chao 2010.11.6. General:. Cheap Enviromentally benign Sustainable Unique reactivity. Genesis:. Kharasch: J. Am. Chem. Soc. 1941 , 63 , 2316. Kochi: J. Am. Chem. Soc. 1971 , 93 , 1487.

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Iron Catalyzed Cross-Coupling Reaction: Recent Advances and Primary Mechanism

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  1. Iron Catalyzed Cross-Coupling Reaction: Recent Advances and Primary Mechanism Wang Chao 2010.11.6

  2. General: Cheap Enviromentally benign Sustainable Unique reactivity

  3. Genesis: Kharasch: J. Am. Chem. Soc.1941, 63, 2316 Kochi: J. Am. Chem. Soc.1971, 93, 1487

  4. Acid chlorides as electrophiles

  5. Alkenyl electrophiles (-)-cubebene (5)

  6. Aryl electrophiles: 菲尔斯特纳Furstner: Angew. Chem., Int. Ed. 2002, 41, 609

  7. allyl, vinyl, and aryl Grignard reagents uniformly led to poor yields in reactions performed with FeX3 (X =Cl, acac) in THF/NMP

  8. a valuable component of liquid-crystalline materials spermidine alkaloid

  9. Masaharu Nakamura: J. AM. CHEM. SOC. 2007, 129, 9844-9845

  10. Alkyl halides the high barrier to oxidative addition b-hydride elimination Nakamura, Eiichi: J. AM. CHEM. SOC. 2004, 126, 3686-3687

  11. Hayashi: Org. Lett. 2004, 6, 1297–1299.

  12. L = TMEDA Angew. Chem. Int. Ed. 2004, 43, 3955 –3957

  13. [FeCl (salen)] Bedford: Chem. Commun.2004, 2822–2823. Cahiez: Angew. Chem. Int. Ed. 2007, 46, 4364 –4366

  14. Iron-Phosphine, -Phosphite, -Arsine, and -Carbene Catalysts Bedford: J. Org. Chem. 2006, 71, 1104-1110

  15. Mechanism for the cross coupling: Kochi, J. J. Org. Chem.1976, 41, 502

  16. Bogdanovic: four-electron reduction, formal constitution [Fe(MgCl)2]n 1:1 mixture of alkene and alkane is formed from the Grignard reagent in the reduction of FeX2, Bogdanovic proposed a -hydride elimination followed by a reductive elimination as two of the elementary steps

  17. 1:1 mixture of alkene and alkane is formed from the Grignard reagent in the reduction of FeX2, Bogdanovic proposed a -hydride elimination followed by a reductive elimination as two of the elementary steps in the formation of [Fe(MgX)2]

  18. Ferrate: 高铁酸盐 J. AM. CHEM. SOC. 2008, 130, 8773–8787

  19. Masaharu Nakamura: Hideo Nagashima: J. AM. CHEM. SOC. 2009, 131, 6078–6079

  20. Radical cyclization rate 1.0x105M-1S-1 Radical ring open rate 1.3x108M-1S-1

  21. Possible catalytic cycle for the (TMEDA)FeAr2-catalyzed crosscoupling reaction.

  22. features: (1) divalent iron (+II oxidation state), (2) neutral complex, (3) coordinatively unsaturated, (4) having sufficient spin density on the iron center. Masaharu Nakamura:J. AM. CHEM. SOC. 2010, 132, 10674–10676

  23. Shi, ZJ: J. AM. CHEM. SOC. 2009, 131, 14656–14657

  24. Oxidative homo-coupling Cahiez: J. AM. CHEM. SOC. 2007, 129, 13788-13789

  25. benzyl-, allyl-, or tertiary alkylzinc give low yields Angew. Chem. Int. Ed. 2009, 48, 2969 –2972

  26. Cross-coupling based on C-H activation/C-C bond formation: Cheap iron and mild condition 0oC J. AM. CHEM. SOC. 2008, 130, 5858–5859

  27. Angew. Chem. Int. Ed. 2009, 48, 2925 –2928

  28. J. AM. CHEM. SOC. 2010, 132, 5568–5569

  29. Yu, XQ: Angew. Chem. Int. Ed. 2008, 47, 8897 –8900 Lei AW: Angew. Chem. Int. Ed. 2010, 49, 2004 –2008

  30. Charette: J. AM. CHEM. SOC. 2010, 132, 1514–1516

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