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React Scales Poster

The document describes how to read reactivity scales that show the reactivity parameters of various electrophiles and nucleophiles. It states that electrophiles and nucleophiles located at similar levels on the scale will react at measurable rates, while those at opposite ends will not react or will only react slowly. The scales allow calculation of rate constants for reactions between electrophiles and nucleophiles using the given equation.
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0% found this document useful (0 votes)
85 views1 page

React Scales Poster

The document describes how to read reactivity scales that show the reactivity parameters of various electrophiles and nucleophiles. It states that electrophiles and nucleophiles located at similar levels on the scale will react at measurable rates, while those at opposite ends will not react or will only react slowly. The scales allow calculation of rate constants for reactions between electrophiles and nucleophiles using the given equation.
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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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

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