How to read the scales:
Reactivity Scales
OSiMe3
H
N2
H
N
H
S
OMe
O
Ph
SiMe3
O
SMe2
O
NHAc
PPh3 N
COMe CO2Et
CO2Et
BF3
OSiMe3
O
CN
COMe CO2Et
SMe2
H
CO2Et
NO2
H
CN
-25
CO2Et
CO2Et
CONMe2
O
k calcd < 10–6 M–1 s–1
-20
no reaction at 20 °C
Electrophilicity Parameter E
Ph
Michael additions
Tsuji-Trost
Ph
-5
O
N
N
Me
Friedel-Crafts
0
10
15
20
OMe
Ph
diffusion control
5
NO2
Ph
H
Ph
F
F
F
-5
N2+
Ph
10
-10
F
F
7
6
-3.65/1.97
-2.94/1.11
Parentheses indicate estimated sN parameters.
-1.00/1.40
+
-0.13/1.21
Ph
(0.25/1.00)
-0.25/1.09
(-0.50/1.10)
0.06/0.71
OSi(C6F5)3
OMe
SiHex3
1.70/1.06
p-Tol
Si(SiMe3)3
1.95/0.98
HSiPh3
O
S
(1.98/1.10)
(1.17/1.00)
S
SiMe3
4.41/0.96
OSiMe3
GePh3
4.67/0.81
SnBu3
(4.74/1.15)
HSiBu3
SnPh3 (5.13/0.90)
SnBu3
Fp
6.78/0.95
6.98/0.85
7.48/0.89
OSiMe3
9.00/0.98
NH
N Me
9.63/0.57
OEt
(H2O)
(H2O)
P(OBu)3
N
10.36/0.70
Cl
(10.50/0.73)
(H2O)
(H2O)
N
OMe
N
Cl
O
11.44/0.68
(H2O)
N
NMe2
N
OMe
N
(H2O)
O
O
(MeCN)
NMe2
N
N
O
15.80/0.66
N
(15.90/0.67)
O
P(4-MeO-C6H4)316.17/0.62
N
16.28/0.67
(MeCN)
N
Ph
–
O
OEt
O
O
O
O
–
O
O
–
O
O
–
(DMSO)
–
O
Ph2P
–
+
N
O2N
–
–
Me2S
CN
18.69/0.72
CO2Et
19.20/0.69
O
OEt
(DMSO)
N
(DMSO)
N
19.46/0.58
Ph
CN
21.07/0.68
(DMSO)
F3C
–
–
SO2CF3
15.06/0.82
N
(DMSO)
18.38/0.72
(DMSO)
NC
F3C
–
O2N
O2N
18.82/0.69
(DMSO)
15.91/0.86
O2N
(DMSO)
17.64/0.73
19.36/0.67
O
14.91/0.86
- OH (H O)
2
tBuNH2
–
NO2–
16.29/0.75
NO2–
16.96/0.73
18.06/0.71
NO2–
18.29/0.71
NH2
SO2CF3 (MeOH)
–
NO2–
NO2–
H
(MeOH)
NH2
O
N
H
[BH4]–
- OOH (H O)
2
H
20.61/0.69
(DMSO)
20.71/0.60
-0.97
MeO
OMe
7
-3.14
CF3
-3.85
N
Ph
CF3
+
N
Me
CF3
+
N
Ph
CF3
+
Ph2N
-5
-6
-7
8
-8
-9
N
-5.89
Me
O2N
N
+
-10.04
NH
O
16.03/0.66
16.83/0.56
O
NH
16.96/0.67
-12
-11.87
-12.18
NH
17.19/0.71
(DMSO)
N
PhSO2–
17.20/0.72
17.94/0.60
14
18.80/0.70
Ph
Ph
16
-16
17
-17
Ph
-18
-19
20.50/0.59
N
20.54/0.60
Me N
20.59/0.52
(DMSO)
(MeCN)
-11.16
-11.31
O
N
CN
N
Cl
CO2Et
CO2Et
O
O
Fe
+
N
EtO
Ph
NC
Ph
CN
+
Ph
O
Pd(P(OPh)3)2
O
O
NC
OMe
O
CN
OMe
t BuO2C N N CO tBu
2
(MeCN)
O2N
NO2
S
NO2
NO2
CN
O
NMe2
Me
N O
O
O
N
N
O
-15.71 Me N
2
N
NH2
O H
N N
Ph
O
+
-O
O
O
CN
NMe2
+
OMe
2
-18.06
Prof. Herbert Mayr, Dr. Armin Ofial
Department Chemie
Ludwig-Maximilians-Universität München
Butenandtstr. 5-13 (Haus F)
81377 München (Germany)
[email protected]
12/2015
OMe
N
N
O
MeO
-17.18
-O
NO -17.67
EtO
EtO
+
Fe
-16.19
EtO
O
N
MeO
-15.38 EtO
-16.36
EtO
O
_
O
N+
O
N
N
-13.19 O N
2
NC
NMe2
-14.68
EtO
NMe2
-20
N
-12.29
-12.33
NMe2
-12.76
O
O
+
-20.55
N
-10.80
O
-17.90
O
+
-7.37
-7.76
OMe
EtO
+
NMe2-13.30
-13.56
-13.90
NC
O
(MeCN)
O
O
+
-18.98
Ph
Co2(CO)5(PPh3)
-14.91
+
Cl
+
-14.10 Me2N
-O
EtO
20
CO2Et
O
-17.29
-19.49
(DMSO)
N
N
N O
Me
O
+
-15.83
-16.11
N
-6.26
-10.11
-10.15
-10.28
N
O
F
-O
19
Ph
-15.03
(DMSO)
20.33/0.64
NMe2
-O
(MeCN)
N3–
Me
+
Ph
-O
18
O
O
+
N
N
O
OMe
Ph
-7.15
+
O
+
OMe
N
-6.69
O
+
-15
NMe2
Fe(CO)2Cp
O
+
O
+
-5.91
-6.19
+
-O
CN
-5.77
Ph
(MeCN)
N
-14
19.60/0.60
–HN-CN
EtO2C
CN
+
-4.95
-5.06
-5.17
O
-O
15
O
N+
O
N
Ph
N
-O
(H2O)
(H2O)
N
Me
+
-13
18.08/0.50
18.13/0.44
+
Ph
(DMSO)
2
Br
N
Me
-O
-13.39
(H2O)
NH
OMe
N
(MeCN)
CO –
-O
O
O
Fe(CO)3
C(Ph)2OSiMe3
-8.37
+
N
Ph
-8.54
+
-8.94
Fe(CO)3
-9.21
OMe
-9.27
-9.42
+
O
Fe(CO)3
N
Me
+
Fe
+
-4.67
_
+
+
N
Me
Br
N
Ph
N
Ph
(H2O)
(DMSO)
NO2– (MeCN)
SCN –(MeCN)
N
+
-11
14.68/0.53
(H2O)
NMe2
+
N
(DMSO)
16.27/0.70
(DMSO)
-8.76
Me2N
+
Fe
+
N
Me
Me
N
O
H
MeO
-3.49
-3.66 Cl
-3.72
Cl
NO2
+
S
Me
N
Ph
14.30/0.67
SO32 –
N
-8.22
13.51/0.58
CN–
N
H
-7.02
S
O
N
Ph
-9.45
-10
N N
N
NPh2
+
O
-8.63
(H2O)
(DMSO)
O2N
N
Me
+
+
S
H3C
-2.90
Fe(CO)3
+
Co2(CO)6
S
-2.57
NO2
-7.69
(H2O)
15.0/0.80
Co2(CO)Ph
6
Me3Si
-2.14
Fe
-4
13.33/0.56
15.40/0.55
15.62/0.54
N
(DMSO)
19.49/0.63
6
12
(MeCN)
+
-1.45
+
O
+
-5.53
10
10.47/0.61
10.48/0.65 (H2O)
13.60/0.84
18.86/0.70
(H2O)
20.72/0.58
(H2O)
OCN –
OEt
+
Co2(CO)6
-0.84
OMe
-4.72
5
12.15/0.65 (DMSO)
Gly-Gly-Gly – 12.26/0.63 (H2O)
12.66/0.59 (H2O)
CF3CH2O13
NH2
13.21 /0.54
18.5/0.75
(MeCN)
-3
11.63/0.95
(DMSO)
SO2Ph
20.22/0.65
(DMSO)
(DMSO)
4
10.67/0.91
N
H
H2NNHCONH2 11.05/0.52 (H2O)11
H2NOH
11.41/0.55 (H2O)
[BH3CN]–
11.52/0.67 (DMSO)
17.33/0.74
SO2CF3 (DMSO)
CO2–
19.50/0.55
(DMSO)
NO2–
N
NC
(DMSO)
3
10.04/0.82
N
H
CF3CH2NH2
OMe
Ph
+
(H2O)
O
-0.25
+
Cr(CO)3
+
-2
9.48/0.59
N
O
OMe
-2.64
9
NH3
O
(H2O)
N
N
SO2CF3 (DMSO)
N
(H2O)
15.57/0.58
(DMSO)
OEt OEt
O
N
Me
+
MeO
-1.60
2
Ph
Cr(CO)3
0.14
O
8.69/1.07
Gly –
13.41/0.82
Ph
+
-1.36
(7.26/1.10)
8.01/0.96
1.07
Ph
Ph
O
-1
N
H
14.33/0.69
O
–
(DMSO)
NO2
19.92/0.67
(DMSO)
–
O
N
(DMSO)
NO2
18.42/0.65
O
Ph2P
–
(H2O)
16.03/0.86
P(4-Me2N-C6H4)318.39/0.64
Me2S
13.36/0.81
14.49/0.86
14.25/0.46
–
–
N
N
(DMSO)
16.27/0.77
O
12.90/0.79
O2N
2
–
N
Me
13.91/0.86
NO –
P(4-Me-C6H4)3 15.44/0.64
15.49/0.69
PBu3
N
O
– O
NO2
15.29/0.70
N
(H2O)
NO2– 13.58/0.52
(13.70/0.67)
14.33/0.65
P(C6H5)3
13.09/0.50
NO2–
O2N
(H2O)
OMe
N
H
12.56/0.70
O
13.19/0.56
N
Me
(H2O)
OPh
+
0.00
+
0.98
MeO
1
1.12
O• BCl3
Ph
+
(6.54/1.10)
12.47/0.52
O
Cl
5.85/1.03
O
11.40/0.83
–N
11.50/0.91
OSiMe3
(12.90/0.67)
N
(MeCN)
N
O
Ph3P=CHCN
12.29/0.75
P(4-Cl-C6H4)3 12.58/0.65
Ph3P=CHCO2Et 12.79/0.77
(MeCN)
10.78/0.89
S
O O
10.61/0.86
OSiMe3
(11.70/0.67)
N
Me
O
–N
5.75/1.23
N
Me
9.00/0.90
Ph
9.72/0.72
4.90/0.74
5.47/0.77
N
Me
8.57/0.84
OMe
CONH2
N
H Me
N H
0
1.44
+
MeO
0
(4.80/0.86)
Ph
PhCH2-N=C:
tBu-N=C:
OSi(C6F5)3
8.16/0.67
8.67/0.82
N
CH2Ph
EtO2C
CO2Et
3.84/0.87
4.76/0.86
N(OSiMe3)2
OSiMe3
10.38/0.87
OSiMe3
OSiMe3
N(OSiMe3)2
OSiMe3
(7.22/1.00)
O
OMe
+
OMe
O • BCl3
0.61
4.23/0.93
6.66/1.02
O
10.21/0.82
OBu
OSiMe3
11.05/0.73
N
9.81/0.81
OEt
OSiMe3
9.91/0.55
CO2Me
N(OSitBuMe2)2
(5.58/1.00)
6.57/0.93
OSiMe3
N(OSiMe3)2
5.02/0.94
8.45/0.83
OMe
N
6.22/0.96
+
1
+
N
2.16
OPh 1.90
OMe
1.48
-1
2.41
2.11
(3.63/1.10)
3.44/0.94
3.93/1.11
N
SnBu3
3.61/1.11
OSiMe3
(4.60/0.90)
8.23/0.81
OPh
O
3.76/0.91
OSiMe3
3.42/0.94
Fe(CO)3
(2.37/1.10)
5.21/1.00
2
+
2.89
+
+
-2
2.48/1.09
(2.20/1.10)
O
OSiMe3
(6.62/1.00)
OSiMe3
(6.77/1.00)
Fp = Fe(CO)2C5H5
N
SiBu3
OMe
2.90
OPh
OMe
O
5.41/0.91
Ph
OSiMe3
(7.69/0.76)
N
H
O
OSiMe3
(4.46/1.15)
OSiMe3
OSiMe3
N
N
SiEt3
(1.53/1.00)
3.20
2.97
+
+
3
1.35/0.99
MeO
+
+
1.33/1.29
4.15
Me
-0.81
SiMe3 (1.33/0.90)
F
Cl
0.34/0.68
(2.16/1.10)
3.99/0.73
OSiMe3
Fp = Fe(CO)2C5H5
NMe2
O
(1.49/1.00)
OSi(i-Pr)3
3.94/1.00
OSiMe3
SiMe3 5.38/0.89
SnBu3 5.46/0.89
SnMe3
Fp
SiMe3
OSi(SiMe3)3
5.07/0.91
6.68/0.81
N
O
-3
Co2(CO)6
SnBu3
+
F
+
Me
(-0.76/0.90)
Ph
Ph
1.10/0.98
(1.17/1.10)
(3.09/1.00)
3.58/0.70
HSiEt3
HSiMe2Ph
3.55/0.75
OSi(i-Pr)3 (3.87/1.00)
2.82/0.89
4.17/0.83
SiMe3
(0.67/1.10
(2.60/1.00)
2.65/0.72
(-0.80/1.00)
Co2(CO)6
-0.44/1.06
(1.77/1.10)
2.30/1.06
(2.60/1.00)
SiPh3
SiMe3
Co2(CO)5(PPh3)
(0.66/1.00)
1.18/1.17
SiMe3
GePh3 (1.20/0.90)
SiMe3 1.68/1.00
3.09/0.90
S
F
3.63
(-1.01/1.10)
0.13/1.27
0.58/0.91
0.90/1.17
1.11/0.98
SnPh3
S
0.06/1.07
0.08/1.15
0.78/0.95
SiMe3
Co2(CO)6
-1.11/0.92
SiMe3
-0.49/1.18
Ph
0.84/1.06
Ph
Further reactivity parameters can be obtained at:
http://www.cup.lmu.de/oc/mayr/DBintro.html
(-0.87/1.00)
0.65/1.17
Ph
OMe
Ph
(-1.07/1.10)
-0.31/0.99
H3SiPh
F
Me
4
-2.44/1.09
Si(SiMe3)3
SiCl3 (-0.57/0.95)
5.01
F
(-2.45/1.10)
(-1.18/1.20)
-1.13/1.46
SiMe3
SiMe2Cl
-0.57/1.06
In CH2Cl2 if not mentioned otherwise.
Nucleophilicity N/sN
CF3
+
5.74
+
-3.57/2.08
-2.77/1.41
6.11
F
4.43
-4
+
6.04
5
-4.36/1.77
Cl
(-1.55/1.10)
F
+
+
25
SiPh3
F
5.20
-5
F
Ph
6.70
CF3
+
F
E = electrophilicity parameter
N = nucleophilicity parameter
sN = nucleophile-specific sensitivity parameter
(N and sN are solvent-dependent)
-1.46/1.05
+
F
6.23
-6
CF3
+
5.47
OSiMe3
F3C
F
+
F
6.87
(7.96)
F
7.52
Nucleophilicity Parameter N
SiMe3
+
F
log k20°C = sN(N + E)
F
+
(8.02)
F
SO2Ph
O
O2N
Ph
Ph
Ph
s–1
SO2Ph
Bn
Co2(CO)6
M–1
O
NMe2
tBu
1010
Ph
O
Ts
N
Ph
k calcd >
5
Ph
H2C NMe2
Nicholas
Hosomi-Sakurai
0
Pd(PPh3)2
NO2
Ph
Mannich
azo couplings
Mukaiyama
8
+
F
E
CO2Et
Ph
-10
• nucleophiles and electrophiles
located on similar levels
combine with measurable rates
(E + N = 0 and k20 °C ≈ 1 M-1 s-1),
• nucleophiles at the top do not
react with the electrophiles at
the bottom, and
• nucleophiles at the bottom react
with the electrophiles at the top
with diffusion control.
CN
EtO2C
-15
The reactivity posters show a selection of the
published reactivity parameters E, N, and sN which
allow the calculation of the rate constants for
combination reactions of electrophiles with
nucleophiles, with the following equation:
CO2Et
H
Electrophilicity E
The compounds are arranged in
such a way that…
NMe2