How to read the scales:

Reactivity Scales The compounds are arranged in

such a way that…
• nucleophiles and electrophiles
Electrophilicity E
located on similar levels
combine with measurable rates +
F F
(E + N = 0 and k20 °C ≈ 1 M-1 s-1), E +
OSiMe3
H N2
O
SMe2
The reactivity posters show a selection of the • nucleophiles at the top do not (8.02) (7.96)
N
H
H
PPh3 N COMe CO2Et
CN published reactivity parameters E, N, and sN which react with the electrophiles at 8 F
+
F
S O O BF3 CO2Et COMe CO2Et F F F3C CF3
OMe
Ph SiMe3 NHAc OSiMe3 SMe2 H NO2 allow the calculation of the rate constants for the bottom, and 7.52
O CO2Et
H CN
-25 CO2Et combination reactions of electrophiles with • nucleophiles at the bottom react
CONMe2 CO2Et with the electrophiles at the top F + +
nucleophiles, with the following equation: with diffusion control. 7 6.87 F F
-20 k calcd < 10–6 M–1 s–1 O
CO2Et 6.70
Michael additions
Ph H CN +
no reaction at 20 °C CO2Et +
CF3
EtO2C
F
Electrophilicity Parameter E

log k20°C = sN(N + E)

Pd(PPh3)2
-15 NO2 F + F
Tsuji-Trost Ph Ph
O
O
Ph
6.23 6.11
Ts
-6 6
Ph N O
+
-10 Ph NMe2
6.04 +
Mannich SO2Ph F F
H2C NMe2 Bn 5.74
azo couplings
Ph N
SO2Ph 5.47 +
-5 Mukaiyama O
N N2+
tBu Me
E = electrophilicity parameter 5.20 +
O2N NO2
Nicholas 5.01
0
Hosomi-Sakurai
Co2(CO)6
Ph
Ph
Ph N = nucleophilicity parameter -5 5 F
Ph Ph OMe + F F
k calcd > 1010 M–1 s–1
Ph
Ph H sN = nucleophile-specific sensitivity parameter 4.43
5 Friedel-Crafts diffusion control F F
(N and sN are solvent-dependent) -4.36/1.77 +
Me F F
4.15
-4 4
F F
10 +
-10 -5 0 5 10 15 20 25 Cl
-3.65/1.97
3.63 Cl
Nucleophilicity Parameter N
Me Me +
-3.57/2.08
+ 3.20
+
OMe 2.97 +
-3 3 2.90
OSiMe3 -2.77/1.41 2.89
-2.94/1.11 OPh
CF3 (-2.45/1.10) + 2.41 +
+
-2.44/1.09 N
(-1.55/1.10) 2.11 2.16
Parentheses indicate estimated sN parameters.

-1.46/1.05 (-1.18/1.20) Co2(CO)6 -2 2 OPh 1.90 +

SiMe3 Ph OMe
-1.13/1.46 OMe -1.11/0.92 OMe
-1.00/1.40 SiMe3 Ph (-1.07/1.10) S SiMe3 + O • BCl3
1.48 1.44
-0.31/0.99 (-0.87/1.00) (-1.01/1.10) Cl +
SiCl3 (-0.57/0.95) Si(SiMe3)3 S OMe 1.12
SiMe3 O• BCl3
Nucleophilicity N/sN

(-0.80/1.00) 1.07
SiMe2Cl -0.25/1.09 (-0.50/1.10) -1 1 + Ph
-0.57/1.06 Co2(CO)5(PPh3) 0.98
0.61 Ph Ph Cr(CO)3
SiPh3 -0.13/1.21 H3SiPh 0.06/0.71 Ph -0.49/1.18 (-0.76/0.90)
SiMe3 +
MeO OPh Ph +
Ph (0.25/1.00) 0.06/1.07 Co2(CO)6 +
0.14 OMe
0.00
0.65/1.17
0.08/1.15
OMe -0.44/1.06 0 0 Ph MeO
0.13/1.27 MeO -0.25
OSi(C6F5)3 Ph 0.34/0.68 OMe +
Ph 0.78/0.95 Ph +
0.58/0.91 Ph +
(0.66/1.00) Co2(CO)6 Cr(CO)3 Co2(CO)6
0.84/1.06 -0.81 -0.84
(0.67/1.10 +
SiMe3
0.90/1.17 1.18/1.17
O SiMe3 (1.33/0.90) 1 -1 O
+
OMe
-0.97
1.33/1.29 Co2(CO)Ph
6
1.11/0.98 SiMe3 1.10/0.98 -1.36
(1.77/1.10) S -1.45
(1.17/1.10) O O + +
GePh3 (1.20/0.90) 1.35/0.99 Me3Si
In CH2Cl2 if not mentioned otherwise.

SiHex3 -1.60 Co2(CO)6

SiMe3 1.68/1.00 (1.17/1.00) S
(1.98/1.10) SnBu3 MeO OMe S
p-Tol 1.70/1.06 (1.53/1.00) 2 -2 + -2.14 + H
2.30/1.06 (1.49/1.00) OMe
Si(SiMe3)3 O MeO S
SiMe3 Fe +
(2.60/1.00) (2.16/1.10) 2.48/1.09 -2.64 -2.57
1.95/0.98 H3C
HSiPh3 2.65/0.72 Fe
(2.60/1.00) O SiEt3
(2.20/1.10) 3.42/0.94
+ -2.90 +
(3.09/1.00) Fe(CO)3 3 -3 CF3 CF3 +
O -3.14 Fe(CO)3 Fe
2.82/0.89 HSiEt3 3.58/0.70 SiBu3
HSiMe2Ph 3.55/0.75 (2.37/1.10) O SnBu3 N N MeO
SnPh3 3.09/0.90 (3.63/1.10) -3.49 O
OSi(i-Pr)3 (3.87/1.00) OSi(i-Pr)3 Ph + Ph +
3.44/0.94 -3.66 Cl CN
N(OSiMe3)2 -3.85 CF3 CF3
OSiMe3 3.94/1.00 O 3.84/0.87 O2N
-3.72
SiPh3 CO2Me 4 -4 N N N N Cl CN
4.17/0.83 HSiBu3 3.61/1.11 N
3.99/0.73 Me Me O
OSiMe3 N(OSitBuMe2)2 + N
SiMe3 4.41/0.96 O 3.76/0.91
(4.46/1.15) 4.23/0.93 NO2
-4.72 O
_
-4.67
GePh3 4.67/0.81 OSiMe3 N(OSiMe3)2 +
3.93/1.11 Ph2N NPh2 O2N N+ -4.95
SnBu3 OSi(SiMe3)3 4.76/0.86 + O
(4.74/1.15) OSiMe3 N(OSiMe3)2
5 -5 O -5.06
5.07/0.91 N + OMe
(4.60/0.90) (4.80/0.86) -5.17 N
SnPh3 (5.13/0.90) OSiMe3 Ph -5.53 N N NO2 Ph
Ph 5.21/1.00 5.02/0.94 O + O S
OSiMe3 PhCH2-N=C: 4.90/0.74 -5.77 +
SiMe3 5.38/0.89 N + Ph
-5.89 N Cl
5.41/0.91 tBu-N=C: 5.47/0.77 Me S
Me -5.91
SnBu3 5.46/0.89
OSiMe3
6 -6 N N + -6.19 +
SnMe3 OSiMe3 5.75/1.23 Ph
6.22/0.96 Ph Ph
(5.58/1.00) N -6.26 Co2(CO)5(PPh3)
6.68/0.81 Ph N NMe2
Me +
OSiMe3 Me -6.69
N 5.85/1.03 Me +
Fp 6.78/0.95 6.57/0.93 6.66/1.02 N
Me -7.02 N
Fp = Fe(CO)2C5H5
(6.54/1.10)
7 -7 Me2N + NMe2
O + -7.15 +
N
6.98/0.85 OSiMe3 O N
NMe2 OSiMe3 Ph
(6.62/1.00) N -7.37
OSiMe3 (7.22/1.00) Ph N
SnBu3 7.48/0.89 Me OMe -7.69 N N _

O + -7.76 O
(6.77/1.00) OSi(C6F5)3 (7.26/1.10) +
N Fe(CO)3 N N+
8.16/0.67 N
N (7.69/0.76) OSiMe3 OSiMe3 H 8 -8 -8.22 C(Ph)2OSiMe3
O
N 8.01/0.96 MeO N N
H 8.23/0.81 8.57/0.84 N N + -8.37
OPh OMe N Me Me N +
Fp H -8.63 + Ph
8.45/0.83 CONH2 Br -8.54 Fe Fe
Fp = Fe(CO)2C5H5 OSiMe3 8.69/1.07 +
8.67/0.82 N -8.76 -8.94
9.00/0.98 N 9 -9 -O OMe Fe(CO)3 +
OMe Me OMe -9.21 N Ph
CH2Ph Br +
N NH 9.63/0.57 NH3 9.48/0.59 -9.27
OEt EtO2C CO2Et -9.45
(H2O) (H2O)
+ -9.42 NC
9.81/0.81 Ph
N N Me 9.91/0.55 OEt 9.00/0.90 N N O Fe(CO)3 CN
N N O 10.04/0.82
(H2O) H Me -10.04 Me + Me +
OSiMe3 10 -10 Ph -10.11 Ph
- OH (H O) 10.47/0.61
P(OBu)3 10.36/0.70 10.21/0.82 N H 2
OBu tBuNH2 10.48/0.65 (H2O) O -10.15 O Pd(P(OPh)3)2
N Ph N N -10.28
N Cl (10.50/0.73) OSiMe3 9.72/0.72 N O
O 10.67/0.91 EtO2C
(H2O) 10.38/0.87 Me (MeCN) N + N CO2Et -10.80
OSiMe3 H (MeCN) O O OMe
–N -11
N 11.05/0.73 OSiMe3 10.78/0.89 H2NNHCONH2 11.05/0.52 (H2O)11 -11.16 NC
(H2O) S (MeCN)
H2NOH N N
O 11.41/0.55 (H2O) + -11.31
10.61/0.86 O O + Fe(CO)2Cp CN
N OMe 11.44/0.68 [BH3CN]– 11.52/0.67 (DMSO) Ph OMe
(H2O) O
N O t BuO2C N N CO tBu
OSiMe3 11.63/0.95 2
N Cl (11.70/0.67) 11.40/0.83 -11.87 -O O (MeCN)
12 -12 O2N
Further reactivity parameters can be obtained at:

O 11.50/0.91 –N N -12.18 Ph O
http://www.cup.lmu.de/oc/mayr/DBintro.html

Ph3P=CHCN 12.29/0.75 12.47/0.52 H + O

(H2O) Ph -12.29
P(4-Cl-C6H4)3 12.58/0.65 OSiMe3 CF3CH2NH2 12.15/0.65 (DMSO) O S NO2
O -12.33
Ph3P=CHCO2Et 12.79/0.77 Gly-Gly-Gly – 12.26/0.63 (H2O) -O OMe NO2
O 12.56/0.70 O O NMe2
-12.76
N 12.90/0.79 CF3CH2O- 12.66/0.59 (H2O) Ph O
N (12.90/0.67)
Me NH2 13.21 /0.54 13 -13 Me
13.09/0.50 (H2O) + N -13.19 O N NO2
N NMe2 13.19/0.56 NO2– 13.36/0.81 NH2 -13.39
Ph 2
(H2O) N 13.33/0.56 NC
(H2O) O2N (H2O) O N O NMe2-13.30
-O NMe2
NO2– 13.58/0.52 Gly – (H2O) 13.51/0.58 Me -13.56 CN
N OMe (13.70/0.67) N O Ph O -13.90 NMe2
(H2O) O
13.41/0.82 OCN – 13.60/0.84 14 -14
O2N (MeCN) N OMe
O O OEt + -14.10 Me2N N
P(C6H5)3 14.33/0.65 13.91/0.86 14.49/0.86 14.30/0.67 F Me
SO2CF3 (DMSO) NH2 NMe2 O
O O
– O (DMSO) – O (DMSO)
O N O
N 14.68/0.53 -O -14.68
NO2 N N O
15.29/0.70 14.91/0.86 H (H2O)
N (MeCN) 14.25/0.46 -15 -15.03 O
(H2O) [BH4]– 15.0/0.80 15 -14.91
(DMSO) + N NH2
P(4-Me-C6H4)3 15.44/0.64 NO – - OOH (H O)
2 N 15.06/0.82 2 15.40/0.55 O N -15.38 EtO N
PBu3 15.49/0.69 O O H
– 14.33/0.69 O NH 15.62/0.54 -O
O O (H2O) (H2O) NC -15.71 Me N N N
-15.83 CN N Ph
N NMe2 15.80/0.66 OEt N 15.91/0.86
2
N 16.03/0.66 O
N
O2N
O O (DMSO) 16 -16 -16.11 + O -16.19
N N (15.90/0.67) O 15.57/0.58 +
–
O O (H2O) NO2–
16.29/0.75 CN– 16.27/0.70
(MeCN)
(DMSO) -O OMe -16.36
16.03/0.86 NC
P(4-MeO-C6H4)316.17/0.62 Ph SO32 – 16.83/0.56 -O NMe2
– (DMSO) 16.96/0.73 (H2O)
N NO2– (DMSO) O +
16.96/0.67 -17 MeO
16.28/0.67 F3C O NH
(DMSO)
17 + O -17.18
N (MeCN) 16.27/0.77 17.33/0.74 -17.29
(DMSO) SO2CF3 (DMSO) EtO -O NMe2
O – O – NH 17.19/0.71 -O
(DMSO) NMe2 OMe
18.06/0.71 EtO O NO -17.67
NO2–
2
P(4-Me2N-C6H4)318.39/0.64 17.64/0.73 NO2– (MeCN) 17.20/0.72 -17.90 O
O O O2N (DMSO)
– (DMSO)
-18 -18.06
NO2 SCN –(MeCN) 17.94/0.60 18 +
EtO
18.29/0.71
18.38/0.72 NO2–
18.42/0.65 O – O
(DMSO)
Me2S (DMSO) O2N CO – 18.08/0.50 EtO O CN
(DMSO) N 2 -O N
O OEt 18.5/0.75 H (H2O)
18.82/0.69 SO2Ph (DMSO)
Ph2P CN 18.69/0.72 – 18.13/0.44
O O (DMSO) NH -18.98
O
– (DMSO) –
N 18.86/0.70
(H2O) 19 -19 O
19.20/0.69 N N 19.36/0.67 (MeCN) 18.80/0.70 Cl Prof. Herbert Mayr, Dr. Armin Ofial
Ph2P CO2Et N N (MeCN) EtO
– (DMSO) –
(DMSO)
NC CO2– -19.49 Department Chemie
N N 19.60/0.60 EtO O
O 19.46/0.58 19.49/0.63 PhSO2– Ludwig-Maximilians-Universität München
+ – 19.50/0.55 SO2CF3 (MeOH) (DMSO)
N (DMSO) (H2O) – 20.33/0.64 Butenandtstr. 5-13 (Haus F)
– Ph –HN-CN
CO2Et
O2N NO2 OEt OEt 20.22/0.65 NO2–
(DMSO) 20 -20 CO2Et 81377 München (Germany)
19.92/0.67 20.61/0.69 N3– 20.50/0.59
(DMSO) (DMSO) (DMSO)
O [email protected]
(DMSO) O – O
– F3C H NO2– N 20.54/0.60 -20.55
20.71/0.60 EtO
CN (MeCN)
20.72/0.58 H
(DMSO) 12/2015
21.07/0.68 SO2CF3 20.59/0.52 EtO O
Me2S (DMSO) – (MeOH) Me N
(MeCN) N