Iron Catalyzed Cross-Coupling Reaction:

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Iron Catalyzed Cross-Coupling Reaction Recent
Advances and Primary Mechanism
Wang Chao 2010.11.6
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General
Cheap Enviromentally benign Sustainable Unique
reactivity
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Genesis
Kharasch J. Am. Chem. Soc. 1941, 63, 2316
Kochi J. Am. Chem. Soc. 1971, 93, 1487
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Acid chlorides as electrophiles
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Alkenyl electrophiles
(-)-cubebene (5)
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Aryl electrophiles
?????Furstner Angew. Chem., Int. Ed. 2002, 41,
609
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allyl, vinyl, and aryl Grignard reagents
uniformly led to poor yields in reactions
performed with FeX3 (X Cl, acac) in THF/NMP
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a valuable component of liquid-crystalline
materials
spermidine alkaloid
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Masaharu Nakamura J. AM. CHEM. SOC. 2007, 129,
9844-9845
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Alkyl halides
the high barrier to oxidative addition b-hydride
elimination
Nakamura, Eiichi J. AM. CHEM. SOC. 2004, 126,
3686-3687
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Hayashi Org. Lett. 2004, 6, 12971299.
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L TMEDA
Angew. Chem. Int. Ed. 2004, 43, 3955 3957
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FeCl (salen)
Bedford Chem. Commun.2004, 28222823.
Cahiez Angew. Chem. Int. Ed. 2007, 46, 4364 4366
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Iron-Phosphine, -Phosphite, -Arsine, and -Carbene
Catalysts
Bedford J. Org. Chem. 2006, 71, 1104-1110
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Mechanism for the cross coupling
Kochi, J. J. Org. Chem. 1976, 41, 502
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Bogdanovic
four-electron reduction, formal constitution
Fe(MgCl)2n 11 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
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11 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
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J. AM. CHEM. SOC. 2008, 130, 87738787
Ferrate ????
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Masaharu Nakamura Hideo Nagashima
J. AM. CHEM. SOC. 2009, 131, 60786079
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Radical cyclization rate 1.0x105M-1S-1
Radical ring open rate 1.3x108M-1S-1
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Possible catalytic cycle for the
(TMEDA)FeAr2-catalyzed crosscoupling reaction.
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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, 1067410676
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Shi, ZJ J. AM. CHEM. SOC. 2009, 131, 1465614657
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Oxidative homo-coupling
Cahiez J. AM. CHEM. SOC. 2007, 129, 13788-13789
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benzyl-, allyl-, or tertiary alkylzinc give low
yields
Angew. Chem. Int. Ed. 2009, 48, 2969 2972
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Cross-coupling based on C-H activation/C-C bond
formation
Cheap iron and mild condition 0oC
J. AM. CHEM. SOC. 2008, 130, 58585859
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Angew. Chem. Int. Ed. 2009, 48, 2925 2928
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J. AM. CHEM. SOC. 2010, 132, 55685569
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Yu, XQ Angew. Chem. Int. Ed. 2008, 47, 8897
8900
Lei AW Angew. Chem. Int. Ed. 2010, 49, 2004
2008
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Charette J. AM. CHEM. SOC. 2010, 132, 15141516