Page 1174 - Advanced Organic Chemistry Part B - Reactions & Synthesis

1150 Interesting hydrocarbon oxidations have been observed using Fe(II) catalysts with
oxygen or hydrogen peroxide as the oxidant. These catalytic systems have become
CHAPTER 12 287
known as “Gif chemistry” after the location of their discovery in France. An
Oxidations improved system involving Fe(III), picolinic acid, and H O has been developed. The
2
2
reactive species generated in these systems is believed to be at the Fe(V)=O oxidation
level. 288 The key step is hydrogen abstraction from the hydrocarbon by this Fe(V)=O
intermediate.
H O 2 H O
2
2
OH
Fe III OH Fe V O
R CH 2
2
R C O OH
2
OH Fe V
CHR 2
Fe III
2
O CHR 2 H O 2
2
OH
1 O + 2 H+
Fe III 2
CHR 2

Oxidation of trans-decalin leads to a mixture of 1- and 2-trans-decalone. 289

H FeCl 3 H O H
H O 2 O
2
+
pyridine
H acetic acid H H
The initial intermediates containing C−Fe bonds can be diverted by reagents such as
CBrCl or CO, among others. 290
3
BrCHR 2
BrCCl 3 HOCHR 2
O OH OH
O
V
Fe + RCH R Fe CHR 2 Fe OOCHR 2
2
R H O
2
– C O + R CHCO H O CR 2
2
2
287 D. H. R. Barton and D. Doller, Acc. Chem. Res., 25, 504 (1992); D. H. R. Barton, Chem. Soc. Rev., 25,
237 (1996); D. H. R. Barton, Tetrahedron, 54, 5805 (1998).
288
D. H. R. Barton, S. D. Beviere, W. Chavasiri, E. Csuhai, D. Doller, and W. G. Liu, J. Am. Chem. Soc.,
114, 2147 (1992).
289 U. Schuchardt, M. J. D. M. Jannini, D. T. Richens, M. C. Guerreiro, and E. V. Spinace, Tetrahedron,
57, 2685 (2001).
290
D. H. R. Barton, E. Csuhai, and D. Doller, Tetrahedron Lett., 33, 3413 (1992); D. H. R. Barton,
E. Csuhai, and D. Doller, Tetrahedron Lett., 33, 4389 (1992).