Abstract
Variation of the activation parameters in the Michael-type reactions (AdN reactions) offers an additive mechanistic tool for the studies of these reactions in solution. This approach uses the substituent effects on the aromatic rings to the variation of the activation parameters, ∆X ≠ (X = H, S, G) in the above reactions in the frameworks of the Hammett-like equations in order to evaluate the resultant δ∆X ≠ reaction constants. The single linear dependences of the internal enthalpy constants δ∆H ≠ int on the δ∆G ≠ and the Hammett ρ constants show that the substituent effects in the substrates and nucleophiles on the mechanistic features in AdN reactions are governed by the magnitude of δ∆H ≠ int when one of the steps of the process is the single rate-determining step.
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Perlmutter P (1992) Conjugate addition reactions in organic synthesis. Pergamon, Oxford
Rossiter BE, Swingle NM (1992) Chem Rev 92:771
Csáky AG, de la Herrán G, Murcia MC (2010) Chem Soc Rev 39:4080
Evans DA, Mito S, Seidel D (2007) J Am Chem Soc 129:11583
Rabalakos C, Wulff WD (2008) J Am Chem Soc 130:13524
Gao P, Wang C, Wu Y, Zhou Z, Tang C (2008) Eur J Org Chem 2008:4563. doi:10.1002/ejoc.200800555
Dong XQ, Teng HL, Wang CJ (2009) Org Lett 11:1265
Tan B, Zhang X, Chua PJ, Zhong G (2009) Chem Commun 779. doi:10.1039/b813915f
Peng L, Xu XY, Wang LL, Huang J, Bai JF, Huang QC, Wang LX (2010) Eur J Org Chem 2010:1849. doi:10.1002/ejoc.200901509
Yu H, Liu M, Han S (2014) Tetrahedron 70:8380
Ma CH, Kang TR, Liu QZ (2014) Eur J Org Chem 2014:3981. doi:10.1002/ejoc.201402243
Fang X, Dong XQ, Wang CJ (2014) Tetrahedron Lett 55:5660
Kwiatkowski J, Lu Y (2014) Chem Commun 50:9313
Kamal A, Sathish M, Srinivasulu V, Chetna J, Shekar KC, Nekkanti S, Tangella Y, Shankaraiah N (2014) Org Biomol Chem 12:8008
Du H, Rodriguez J, Bugaut X, Constantieux T (2014) Chem Eur J 20:8458
Kawazoe S, Yoshida K, Shimazaki Y, Oriyama T (2015) Tetrahedron Lett 56:410
Işik M, Unver MY, Tanyeli C (2015) J Org Chem 80:828
Bernasconi CF (1989) Tetrahedron 45:4017
Bernasconi CF, Schuck DF (1992) J Org Chem 57:2365
Bernasconi CF, Pérez-Lorenzo M, Codding SJ (2007) J Org Chem 72:9456
Kim SI, Baek HW, Um IH (2009) Bull Korean Chem Soc 30:2909
Kim SI, Hwang SJ, Park YM, Um IH (2010) Bull Korean Chem Soc 31:1199
Lee I (1995) Chem Soc Rev 24:223
Leffler JE, Grunwald E (1963) Rates and equilibria of organic reactions. Wiley, New York
Hansch C, Leo A, Taft RW (1991) Chem Rev 91:165
Ammal SC, Mishima M, Yamataka H (2003) J Org Chem 68:7772
Itoh S, Yamataka H (2011) Chem Eur J 17:1230
Um IH, Kang JS, Park JY (2013) J Org Chem 78:5604
Oh HK, Lee JM, Sung DD, Lee I (2005) J Org Chem 70:3089
Vlasov VM (2010) New J Chem 34:1408
Vlasov VM (2012) J Phys Org Chem 25:296
Hepler LG (1963) J Am Chem Soc 85:3089
Hepler LG (1971) Can J Chem 49:2803
Ruff F (2004) Internet Electron J Des 3:474
Fábián A, Ruff F, Farkas Ö (2008) J Phys Org Chem 21:988
Exner O (1973) Prog Phys Org Chem 10:411
Liu L, Guo QX (2001) Chem Rev 101:673
Oh HK, Yang JH, Sung DD, Lee I (2000) J Chem Soc Perkin Trans 2: 101
Oh HK, Kim TS, Lee HW, Lee I (2002) J Chem Soc Perkin Trans 2: 282
Oh HK, Kim IK, Sung DD, Lee I (2005) Bull Korean Chem Soc 26:641
Sung DD, Kang SS, Lee JP, Jung DI, Ryu ZH, Lee I (2007) Bull Korean Chem Soc 28:1670
Oh HK, Kim IK, Lee HW, Lee I (2004) J Org Chem 69:3806
Oh HK, Kim IK, Sung DD, Lee I (2004) Org Biomol Chem 2:1213
Oh HK, Ku MH (2006) Bull Korean Chem Soc 27:1873
Oh HK, Yang JH, Hwang YH, Lee HW, Lee I (2002) Bull Korean Chem Soc 23:221
Oh HK (2009) Bull Korean Chem Soc 30:1887
Oh HK, Lee JM (2002) Bull Korean Chem Soc 23:1459
Oh HK (2008) Bull Korean Chem Soc 29:1195
Oh HK, Yang JH, Lee HW, Lee I (2000) J Org Chem 65:2188
Hwang J, Yang K, Koo IS, Sung DD, Lee I (2006) Bull Korean Chem Soc 27:733
Oh HK, Ku MH, Lee HW (2005) Bull Korean Chem Soc 26:935
Ku MH, Oh HK, Ko S (2007) Bull Korean Chem Soc 28:1217
Oh HK, Yang JH, Lee HW, Lee I (2000) J Org Chem 65:5391
Oh HK, Kim TS, Lee HW, Lee I (2003) Bull Korean Chem Soc 24:193
Pisareva VS, Korzhova NV, Kazhantseva VM, Korshunov SP (1975) Russ J Org Chem 11:1034
Zenz I, Mayr H (2011) J Org Chem 76:9370
Sarathi PA, Gnanasekaran C, Schunmugasundaram A (2008) Bull Korean Chem Soc 29:790
Kaumanns O, Lucius R, Mayr H (2008) Chem Eur J 14:9675
Um IH, Lee EJ, Seok JA, Kim KH (2005) J Org Chem 70:7530
Um IH, Hwang SJ, Lee EJ (2008) Bull Korean Chem Soc 29:767
Varghese B, Kothari S, Banerji KK (1999) Int J Chem Kinet 31:245
Korzhova NV, Pisareva VS, Korshunov SP (1975) Russ J Org Chem 11:1030
Tselinskii IV, Kolesetskaya GI (1971) Org React (Tartu) 8:79
Lakhdar S, Goumont R, Berionni G, Boubaker T, Kurbatov S, Terrier F (2007) Chem Eur J 13:8317
Um IH, Yuk SM, Yoon SI (2000) Bull Korean Chem Soc 21:553
Um IH, Lee EJ, Min JS (2001) Tetrahedron 57:9585
Dhahri N, Boubaker T, Goumont R (2013) Int J Chem Kinet 45:763
Varghese B, Kothari S, Banerji KK (1998) J Chem Res (M) 1853
Korzhova NV, Korshunov SP, Statsyuk VE, Bodrikov IV (1982) Izv Vysh Uchebn Zaved. Khim Khim Tekhnol (Russ) 25:813
Anslyn EV, Dougherty DA (2006) Modern physical organic chemistry. University Science Books, Sausalito
Lee I, Lee HW (1999) Collect Czech Chem Commun 64:1529
Lee I (1990) Chem Soc Rev 19:317
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Vlasov, V.M. Effects of substituents on activation parameter changes in the Michael-type reactions of nucleophilic addition to activated alkenes and alkynes in solution. Monatsh Chem 147, 319–328 (2016). https://doi.org/10.1007/s00706-015-1622-5
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DOI: https://doi.org/10.1007/s00706-015-1622-5