N
N
Ir
Cl
S O
O
N
N
N
CF 3
D
D
H
H
H
N
N
Ir
Cl
S
O
O
NH 2
N
N
CF 3
H
D
D
60a
60b
60a
60b
ΔG / kcal mol -1
Gbind
G CH-act (b)
G CH-act ( a)
Ir
Cl
N
N
Mes
Mes
59 (6.5 mol%)
53a (6.5 mol%)
58; Celecoxib
S NH 2
O O
N
S NH 2
O O
N
D
a
D
a
N
N
S NH 2
O O
N
N
D b
D b
D 2 (1 atm)
DCM, 2 h
F 3 C
F 3 C
F 3 C
58a
58b
Binding energy is
product
determining
Scheme 17 DFT-calculated rationale for directing group selectivity using catalyst 59 and sulfonamide drug 58
Scheme 18 Counter-anion effects explored in iridium-catalyzed ortho-directed HIE
Iridium Catalysts for Hydrogen Isotope Exchange
285
N
Ir
Cl
S O
O
N
N
N
CF 3
D
D
H
H
H
N
N
Ir
Cl
S
O
O
NH 2
N
N
CF 3
H
D
D
60a
60b
60a
60b
ΔG / kcal mol -1
Gbind
G CH-act (b)
G CH-act ( a)
Ir
Cl
N
N
Mes
Mes
59 (6.5 mol%)
53a (6.5 mol%)
58; Celecoxib
S NH 2
O O
N
S NH 2
O O
N
D
a
D
a
N
N
S NH 2
O O
N
N
D b
D b
D 2 (1 atm)
DCM, 2 h
F 3 C
F 3 C
F 3 C
58a
58b
Binding energy is
product
determining
Scheme 17 DFT-calculated rationale for directing group selectivity using catalyst 59 and sulfonamide drug 58
Scheme 18 Counter-anion effects explored in iridium-catalyzed ortho-directed HIE
Iridium Catalysts for Hydrogen Isotope Exchange
285