O OSiMe OSiMe OSiMe N N N S O O O OSiMe OSiiPr SiMe Ph OMe S S SnBu SnBu SnBu SnPh GePh SiMe SiPh SnBu SnPh SiPh SiMe SiMe GePh pTol NOSiMe NOSitBuMe NOSiMe FeCO NOSiMe MeOOMe SiMe CO SiMe ID: 149397
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O OSiMe OSiMe OSiMe N N N S O O O OSiMe OSi(i-Pr) SiMe Ph OMe S S SnBu SnBu SnBu SnPh GePh SiMe SiPh SnBu SnPh SiPh SiMe SiMe GePh p-Tol N(OSiMe N(OSitBuMe N(OSiMe Fe(CO) N(OSiMe MeOOMe SiMe (CO) SiMe (CO)(PPh (CO) SiMe (CO) OSiMe O OSiMe OSiMe OSiMe OSiMe OSiMe OSiMe OSiMe OSiMe OPh OSiMe OSiMe OSiMe OSiMe OSi(i-Pr) SiMe SiHex SiMe SiCl SiEt O SiBu SnBu SiMe N O N N O N N Cr(CO) (CO) (CO) Ph OPh O BCl Ph O BCl O OEt OEtOEt OSiMe OBu OSiMe OSiMe O OSiMe NH NMe N N NMe N N N H OMe O O O O O O O OEt N O O O2N O2N O2N O O N O OEt HH N N O O OEtOEt OPh N NMe N N N O O N N N OPh N Ph N N Me N Me O Cr(CO) Br NMe N O NMe O N O O N N N N N O Cl CNCN OMe 3C (CO)(PPh Fe(CO) SS (CO) Fe Fe(CO) + Fe(CO) + Pd(P(OPh) + N N NON MeO +_ Fe(CO) + SS H+ CN NMe O2N Fe(CO) S O2N NNNN O2N NON O O2N+_ NMe O O O O O N N NN 2N F3C F3C N O O OMe NN Me O O NMe OO O O NMe OO O O H N H N H NNO N N N N OSi(C 2N CONH O EtO O O EtO O EtO O EtO N O C(Ph)OSiMe H C P P O F O NMe O NMe N Me NNH HNN N O O EtO N O O NH N N Si(SiMe OSi(SiMe O O S S N EtO N BuOtBu F F F F F MeMe F F F F F F F3C F F O F F F OSiMe OSi(C N Si(SiMe SiMe SiMe SiMe O O O O O SnMe N 7.22/1.00 5.58/1.00 11.40/0.838.57/0.8413.36/0.8112.90/0.7910.78/0.89 4.60/0.90 3.09/0.903.44/0.943.61/1.113.76/0.912.82/0.89(2.16/1.10) -1.55/1.10 (-1.07/1.10)-0.49/1.18(-0.87/1.00)(-0.50/1.10)(-1.18/1.20)0.13/1.270.06/1.07(0.66/1.00)(0.67/1.101.35/0.991.33/1.291.10/0.98(1.17/1.10)(1.53/1.00)(5.13/0.90)5.46/0.897.48/0.894.67/0.814.41/0.964.17/0.83(4.74/1.15)-0.13/1.210.65/1.170.78/0.950.90/1.170.84/1.06 0.25/1.00 1.68/1.00(1.20/0.90)1.70/1.061.11/0.98(1.17/1.00)(1.49/1.00)4.23/0.934.76/0.86(4.80/0.86)3.42/0.943.84/0.872.48/1.09-1.11/0.92 -0.76/0.90 -0.44/1.060.34/0.68 1.33/0.90 2.60/1.00 10.61/0.8612.56/0.705.21/1.005.41/0.916.57/0.936.22/0.96 6.77/1.00 6.62/1.00 9.00/0.988.23/0.81 4.46/1.15 3.94/1.00(3.87/1.00)(3.09/1.00)2.30/1.06 2.60/1.00 0.08/1.150.58/0.91 1.98/1.10 1.77/1.10 1.18/1.17-0.25/1.09-0.57/1.06-1.00/1.40 -0.57/0.95 (2.20/1.10)(2.37/1.10)(3.63/1.10) -0.80/1.00 -1.01/1.10 5.02/0.9410.04/0.82HSiPh2.65/0.72SiPh0.06/0.71HSiMePh3.55/0.75HSiEt3.58/0.70HSiBu3.99/0.7315.06/0.8215.91/0.8613.41/0.8214.91/0.8613.91/0.8616.27/0.7717.64/0.7318.82/0.6919.36/0.67(DMSO)(DMSO)(DMSO)(DMSO)(DMSO)P(OBu)10.36/0.7012.58/0.6514.33/0.6515.49/0.6916.17/0.6215.44/0.64-13-11-12-10-14-15-17-16-18-19NNHCONH10.47/0.6111.05/0.5212.15/0.6512.66/0.5913.33/0.5614.30/0.6716.03/0.6616.96/0.6715.40/0.55-7.022.902.111.480.610.00-1.36-2.64-3.14-3.85-4.72-5.53-5.89-7.69-8.22-8.63-8.76-9.45-10.04-12.18-13.39-15.83-16.11-17.29-17.9018.39/0.649.81/0.8110.21/0.8210.38/0.8711.50/0.9116.27/0.7016.83/0.5617.94/0.60(MeCN)17.19/0.7118.38/0.72(DMSO)16.29/0.75(DMSO)16.96/0.73(DMSO)18.06/0.71(DMSO)18.29/0.71(DMSO)18.5/0.75(DMSO)13.09/0.5013.58/0.5214.25/0.4614.33/0.6915.57/0.588.45/0.83Fp = Fe(CO)6.78/0.95Fp = Fe(CO)-0.97-0.84-0.250.140.981.121.441.902.162.412.892.973.201.0717.20/0.72(MeCN)-2020.61/0.69(DMSO)20.71/0.60(DMSO)19.50/0.5520.22/0.65(DMSO)13.21 /0.54(DMSO)(DMSO)(DMSO)(DMSO)(DMSO)9.48/0.5914.68/0.5315.62/0.5413.51/0.5811.41/0.55BuNH10.48/0.6518.13/0.44P(4-Me-C15.80/0.66P(4-Cl-C 13.70/0.67 12.90/0.67 11.70/0.67 10.50/0.73 11.05/0.7313.19/0.56 15.90/0.67 11.44/0.6820.50/0.59(DMSO)(MeCN)5.75/1.23(6.54/1.10)PhCH-N=C:Bu-N=C:4.90/0.745.47/0.775.85/1.03(7.26/1.10)-1.45-9.42-10.80-13.30-13.19-5.06-11.16-10.11-8.94-8.54-7.76-8.37-7.15-6.69-6.26-6.19-5.77-5.17-5.91-4.95-3.72-3.49-2.90-2.57-2.14-1.60-12.33-9.21-4.67-13.56-14.68-11.3118.80/0.70(MeCN)20.54/0.60(MeCN)14.49/0.86(DMSO)19.49/0.63(MeOH)17.33/0.74(DMSO)20.72/0.58(MeOH)-13.90-12.76-10.28-9.278.01/0.968.69/1.0710.67/0.9111.63/0.9518.08/0.50Gly-Gly-Gly12.26/0.6319.92/0.67(DMSO)P(4-MeO-C16.28/0.67(MeCN)15.29/0.70(MeCN)13.60/0.84Gly (H8.16 0.67-18.06-17.67-18.98-20.556.66/1.02-7.373.93/1.118.67/0.829.00/0.90[BH[BH15.0/0.80(DMSO)11.52/0.67(DMSO)12.29/0.75P=CHCN12.79/0.77P=CHCO19.20/0.69(DMSO)18.69/0.72(DMSO)19.46/0.58(DMSO) 0.70(MeCN)-10.15(MeCN)(MeCN)-12.295.475.204.433.635.016.045.74(8.02)6.236.877.526.70(7.96)4.15-0.816.11-3.57/2.08-4.36/1.77-3.65/1.97-2.77 1.41-2.44 1.09 -2.45 1.10 (MeCN)OH -2.94/1.116.98/0.85(MeCN)-0.31/0.99-1.46/1.05-1.13/1.465.38/0.89-16.19-15.71-3.66-14.10-19.496.68/0.8116.03/0.86(DMSO) (CO) -25-10-50510152025ElectrophilicityParameterNucleophilicityParameter NHAc PPh SMe 2 OSiMe SiMe OSiMe COMeCOMe H 2 2+ 2N Pd(PPh CNMe calcd0noreactionat20°Ccalcdá´10diffusioncontrolMichaeladditionsTsuji-TrostMannichazocouplingsMukaiyamaNicholasHosomi-SakuraiFriedel-Crafts OMe CONMe EtO Reactivity ScalesElectrophilicity Further reactivity parameters can be obtained at:http://www.cup.lmu.de/oc/mayr/DBintro.html nucleophiles and electrophiles located on similar levels combine with measurable rates= 0 and nucleophiles at the top do not reactwith the electrophiles at the bottom, andnucleophiles at the bottom react with the electrophiles at the top with diffusion controlHow to read the scales:The compounds are arranged in such a way that In CHif not mentioned otherwise. = electrophilicity parameter= nucleophilicity parameter= nucleophile-specific sensitivity parameterare solvent-dependent)Thereactivitypostersshowaselectionofthepublishedreactivityparameters,andwhichallowthecalculationoftherateconstantsforcombinationreactionsofelectrophileswithnucleophiles,withthefollowingequation:Parentheses indicate estimated sparameters. Prof. Herbert Mayr, Dr. Armin OfialDepartment ChemieLudwig-Maximilians-Universität MünchenButenandtstr. 5-13 (Haus F)81377 München (Germany)Herbert.Mayr@cup.lmu.de