9
Carbene
formation
via TS6
O-H insertion
via TS7
10
Ph
O
F
O Ph
OH
I
Ph
O
[Rh]
Ph
O
[Rh]
O
H
Ph
Proton
transfer
via TS8
Ph
OH
O
[Rh]
Ph
OH
I
F
Ph
O
O
Ph
[Rh]
O
I
F
Ph
O
O
Ph
[Rh]
H
Proton
transfer /
Electrophilic addition
via TS9
Isomerization
via TS10
Ligand coupling
via TS11
TS9
Ph
O
N
2
[Rh]
O
I
F
[Rh]
1
11
Int5
Int6
Int7
Int8
Int9
Int10
Int12
1
N
2
OH
I
F
Ph
O
O
Ph
[Rh]
OH
I
F
Ph
O
O
Ph
[Rh]
Int11
Coordination
change
F
Ph
O
O
Ph
[Rh]
Int13
9
0.0
Ph
O
N
2
[Rh]
Ph
O
[Rh]
O
Ph
H
Ph
O
[Rh]
O
H
Ph
OH
I
F
Ph
O
O
Ph
[Rh]
OH
I
F
Ph
O
O
Ph
[Rh]
4.1
TS6
22.6
5.6
TS7
8.1
-7.1
-5.0
-31.0
-10.7
-29.0
-32.2
TS10
-26.4
-42.9
TS11
-33.1
-70.2
Ligand
exchange
[Rh] =
O
I
F
O
Rh
O
O
O
O
Rh
O
O
O
TS8
Scheme 5
Catalytic cycle of Rh-catalyzed oxyfluorination using hypervalent
fluoroiodine reagent proposed on the basis of DFT calculations. Red numbers are
calculated Gibbs energies (kcal/mol) for each intermediate and transition state relative to Int5
[81]
Mechanisms of Metal-Catalyzed Electrophilic F/CF 3 /SCF 3 Transfer Reactions. . .
47