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

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)

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

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

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

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

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

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

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

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

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

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

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

24. 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

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

31. 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

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