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

4. Acid chlorides as electrophiles

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

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

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

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

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

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

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

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

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

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

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

18. 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

19. 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]

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

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

22. Radical cyclization rate 1.0x10 5 M -1 S -1 Radical ring open rate 1.3x10 8 M -1 S -1

23. Possible catalytic cycle for the (TMEDA)FeAr 2 -catalyzed crosscoupling reaction.

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

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

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

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

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

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

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

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

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