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Synlett 2014; 25(13): 1803-1816
DOI: 10.1055/s-0033-1341280
DOI: 10.1055/s-0033-1341280
account
Reaction Pathways of Alkoxyl Radicals. The Role of Solvent Effects on C–C Bond Fragmentation and Hydrogen Atom Transfer Reactions
Further Information
Publication History
Received: 30 January 2014
Accepted after revision: 17 March 2014
Publication Date:
21 May 2014 (online)
Abstract
This account describes the results of our recent mechanistic studies on unimolecular C–C bond fragmentation (β-scission and O-neophyl rearrangement) and bimolecular hydrogen atom transfer (HAT) reactions of alkoxyl radicals. Particular attention is devoted to the study of solvent effects on these reactions by means of time-resolved techniques such as laser flash photolysis. Information is provided on the effect of ring substituents and of the solvent on the spectral properties of arylcarbinyloxyl radicals and on their reactivity in β-scission and O-neophyl rearrangement reactions, showing that a change in solvent can influence the fragmentation reactivity and selectivity. Detailed information has also been obtained on the role of the substrate structure and of the solvent on HAT reactions involving the cumyloxyl radical, showing the importance of solvent hydrogen bond interactions with the substrate and/or the radical on these processes, and providing a general mechanistic description of the kinetic solvent effects observed in HAT reactions from C–H bonds, as well as expanding on the previously available description for HAT from phenolic O–H bonds. The possible application of these findings to synthetically useful C–H functionalization procedures is discussed.
1 Introduction
2 C–C β-Scission Reactions
3 O-Neophyl Rearrangement
4 Hydrogen Atom Transfer (HAT) Reactions
5 Concluding Remarks
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References
- 1 Orlando JJ, Tyndall GS, Wallington TJ. Chem. Rev. 2003; 103: 4657
- 2 Yin H, Xu L, Porter NA. Chem. Rev. 2011; 111: 5944
- 3 Chaturvedi D, Goswami A, Saikia PP, Barua NC, Rao PG. Chem. Soc. Rev. 2010; 39: 435
- 4 Radicals in Organic Synthesis . Renaud P, Sibi MP. Wiley-VCH; Weinheim: 2001
- 5a Marque SR. A, Siri D. ChemPhysChem 2012; 13: 703
- 5b Nakamura T, Watanabe Y, Suyama S, Tezuka H. J. Chem. Soc., Perkin Trans. 2 2002; 1364
- 5c Newcomb M, Daublain P, Horner JH. J. Org. Chem. 2002; 67: 8669
- 5d Wilsey S, Dowd P, Houk KN. J. Org. Chem. 1999; 64: 8801
- 5e Banks JT, Scaiano JC. J. Am. Chem. Soc. 1993; 115: 6409
- 5f Avila DV, Brown CE, Ingold KU, Lusztyk J. J. Am. Chem. Soc. 1993; 115: 466
- 6 DiLabio GA, Ingold KU, Lin S, Litwinienko G, Mozenson O, Mulder P, Tidwell TT. Angew. Chem. Int. Ed. 2010; 49: 5982
- 7a Čeković Z. Tetrahedron 2003; 59: 8073
- 7b Horner JH, Choi S.-Y, Newcomb M. Org. Lett. 2000; 2: 3369
- 8a Salamone M, DiLabio GA, Bietti M. J. Am. Chem. Soc. 2011; 133: 16625
- 8b Finn M, Friedline R, Suleman NK, Wohl CJ, Tanko JM. J. Am. Chem. Soc. 2004; 126: 7578
- 8c Pischel U, Nau WM. J. Am. Chem. Soc. 2001; 123: 9727
- 8d Paul H, Small RD. Jr, Scaiano JC. J. Am. Chem. Soc. 1978; 100: 4520
- 9a Kempter I, Groß A, Hartung J. Tetrahedron 2012; 68: 12378
- 9b Nunes PM, Estacío SG, Lopes GT, Agapito F, Santos RC, Costa Cabral BJ, Borges dos Santos RM, Martinho Simões JA. J. Phys. Chem. A 2009; 113: 6524
- 10a Bietti M, Calcagni A, Salamone M. J. Org. Chem. 2010; 75: 4514
- 10b Marque S, Tordo P. Top. Curr. Chem. 2005; 250: 43
- 10c Ding B, Bentrude WG. J. Am. Chem. Soc. 2003; 125: 3248
- 10d Ollivier C, Renaud P. Chem. Rev. 2001; 101: 3415
- 10e Griller D, Ingold KU, Patterson LK, Scaiano JC, Small RD. Jr. J. Am. Chem. Soc. 1979; 101: 3780
- 11a Bietti M, DiLabio GA, Lanzalunga O, Salamone M. J. Org. Chem. 2011; 76: 1789
- 11b Bietti M, DiLabio GA, Lanzalunga O, Salamone M. J. Org. Chem. 2010; 75: 5875
- 12a Avila DV, Ingold KU, Di Nardo AA, Zerbetto F, Zgierski MZ, Lusztyk J. J. Am. Chem. Soc. 1995; 117: 2711
- 12b Avila DV, Lusztyk J, Ingold KU. J. Am. Chem. Soc. 1992; 114: 6576
- 13 Walling C. Pure Appl. Chem. 1967; 15: 69
- 14a Bietti M, Lanzalunga O, Salamone M. J. Org. Chem. 2005; 70: 1417
- 14b Aureliano Antunes CS, Bietti M, Lanzalunga O, Salamone M. J. Org. Chem. 2004; 69: 5281
- 15 Bietti M, Gente G, Salamone M. J. Org. Chem. 2005; 70: 6820
- 16 Baciocchi E, Bietti M, Salamone M, Steenken S. J. Org. Chem. 2002; 67: 2266
- 17 Salamone M, Bietti M, Calcagni A, Gente G. Org. Lett. 2009; 11: 2453
- 18 Baciocchi E, Bietti M, Lanzalunga O, Steenken S. J. Am. Chem. Soc. 1998; 120: 11516
- 19 Abraham MH, Grellier PL, Prior DV, Duce PP, Morris JJ, Taylor PJ. J. Chem. Soc., Perkin Trans. 2 1989; 699
- 20 Reichardt C, Welton T. Solvents and Solvent Effects in Organic Chemistry . Wiley-VCH; Weinheim: 2010. 4th ed
- 21 Neta P, Dizdaroglu M, Simic MG. Isr. J. Chem. 1984; 24: 25
- 22a Weber M, Fischer H. J. Am. Chem. Soc. 1999; 121: 7381
- 22b Tsentalovich YP, Kulik LV, Gritsan NP, Yurkovskaya AV. J. Phys. Chem. A 1998; 102: 7975
- 22c Erben-Russ M, Michel C, Bors W, Saran M. J. Phys. Chem. 1987; 102: 2362
- 23 Salamone M, Mangiacapra L, DiLabio GA, Bietti M. J. Am. Chem. Soc. 2013; 135: 415
- 24a Baroudi A, Alicea J, Flack P, Kirincich J, Alabugin IV. J. Org. Chem. 2011; 76: 1521
- 24b Baroudi A, Flack P, Alabugin IV. Chem. Eur. J. 2010; 16: 12316
- 24c Baroudi A, Alicea J, Alabugin IV. Chem. Eur. J. 2010; 16: 7683
- 24d Liu X, Xiong F, Huang X, Xu L, Li P, Wu X. Angew. Chem. Int. Ed. 2013; 52: 6962
- 24e Egami H, Shimizu R, Usui Y, Sodeoka M. Chem. Commun. 2013; 49: 7346
- 24f Studer A, Bossart M. Tetrahedron 2001; 57: 9649
- 25 Bietti M, Calcagni A, Cicero DO, Martella R, Salamone M. Tetrahedron Lett. 2010; 51: 4129
- 26a Bietti M, Ercolani G, Salamone M. J. Org. Chem. 2007; 72: 4515
- 26b Smeu M, DiLabio GA. J. Org. Chem. 2007; 72: 4520
- 27 Aureliano Antunes CS, Bietti M, Ercolani G, Lanzalunga O, Salamone M. J. Org. Chem. 2005; 70: 3884
- 28 Newcomb M, Johnson CC, Manek MB, Varick TR. J. Am. Chem. Soc. 1992; 114: 10915
- 29 Bietti M, Salamone M. J. Org. Chem. 2005; 70: 10603
- 30 Bietti M, Fiorentini S, Pèrez Pato I, Salamone M. J. Org. Chem. 2006; 71: 3167
- 31a Saouma CT, Mayer JM. Chem. Sci. 2014; 5: 21
- 31b Dietl N, Schlangen M, Schwarz H. Angew. Chem. Int. Ed. 2012; 51: 5544
- 31c Lai W, Li C, Chen H, Shaik S. Angew. Chem. Int. Ed. 2012; 51: 5556
- 31d Mayer JM. Acc. Chem. Res. 2011; 44: 36
- 32 Halliwell B, Gutteridge JM. C. Free Radicals in Biology and Medicine . Oxford University Press; Oxford: 2007. 4th ed
- 33a Amorati R, Valgimigli L. Org. Biomol. Chem. 2012; 10: 4147
- 33b Lucarini M, Pedulli GF. Chem. Soc. Rev. 2010; 39: 2106
- 33c Litwinienko G, Ingold KU. Acc. Chem. Res. 2007; 40: 222
- 33d Bowry VW, Ingold KU. Acc. Chem. Res. 1999; 32: 27
- 34a Shaik S, Lai W, Chen H, Wang Y. Acc. Chem. Res. 2010; 43: 1154
- 34b Ortiz de Montellano PR. Chem. Rev. 2010; 110: 932
- 34c Frey PA, Hegeman AD, Reed GH. Chem. Rev. 2006; 106: 3302
- 35a Wei W.-T, Zhou M.-B, Fan J.-H, Liu W, Song R.-J, Liu Y, Hu M, Xie P, Li J.-H. Angew. Chem. Int. Ed. 2013; 52: 3638
- 35b Sibi MP, Landais Y. Angew. Chem. Int. Ed. 2013; 52: 3570
- 35c Gormisky PE, White MC. J. Am. Chem. Soc. 2013; 135: 14052
- 35d Gephart RT. III, McMullin CL, Sapiezynski NG, Jang ES, Aguila MJ. B, Cundari TR, Warren TH. J. Am. Chem. Soc. 2012; 134: 17350
- 35e White MC. Science 2012; 335: 807
- 35f Boess E, Schmitz C, Klussman M. J. Am. Chem. Soc. 2012; 134: 5317
- 35g Michaudel Q, Thevenet D, Baran PS. J. Am. Chem. Soc. 2012; 134: 2547
- 36a Franchi P, Lucarini M, Pedulli GF, Valgimigli L, Lunelli B. J. Am. Chem. Soc. 1999; 121: 507
- 36b Kim SS, Kim SY, Ryou SS, Lee CS, Yoo KH. J. Org. Chem. 1993; 58: 192
- 36c Lalevée J, Allonas X, Fouassier JP. J. Org. Chem. 2007; 72: 6434
- 36d Chatgilialoglu C, Ingold KU, Lusztyk J, Nazran AS, Scaiano JC. Organometallics 1983; 2: 1332
- 37a Salamone M, Martella R, Bietti M. J. Org. Chem. 2012; 77: 8556
- 37b Salamone M, DiLabio GA, Bietti M. J. Org. Chem. 2011; 76: 6264
- 37c Griller D, Howard JA, Marriott PR, Scaiano JC. J. Am. Chem. Soc. 1981; 103: 619
- 38a Malatesta V, Scaiano JC. J. Org. Chem. 1982; 47: 1455
- 38b Beckwith AL. J, Easton CJ. J. Am. Chem. Soc. 1981; 103: 615
- 38c Malatesta V, Ingold KU. J. Am. Chem. Soc. 1981; 103: 609
- 39a Mitroka S, Zimmeck S, Troya D, Tanko JM. J. Am. Chem. Soc. 2010; 132: 2907
- 39b Roberts BP. Chem. Soc. Rev. 1999; 28: 25
- 39c Russell GA. Reactivity, Selectivity, and Polar Effects in Hydrogen Atom Transfer Reactions. In Free Radicals. Vol. 1. Kochi JK. Wiley-Interscience; New York: 1973: 275-331
- 40 Bietti M, Martella R, Salamone M. Org. Lett. 2011; 13: 6110
- 41 Salamone M, DiLabio GA, Bietti M. J. Org. Chem. 2012; 77: 10479
- 42 Luo Y.-R. Comprehensive Handbook of Chemical Bond Energies. CRC Press; Boca Raton: 2007
- 43a Bietti M, Salamone M. Org. Lett. 2010; 12: 3654
- 43b Koner AL, Pischel U, Nau WM. Org. Lett. 2007; 9: 2899
- 44a Salamone M, Giammarioli I, Bietti M. J. Org. Chem. 2011; 76: 4645
- 44b Chatgilialoglu C, Lunazzi L, Macciantelli D, Placucci G. J. Am. Chem. Soc. 1984; 106: 5252
- 45 Salamone M, Milan M, DiLabio GA, Bietti M. J. Org. Chem. 2013; 78: 5909
- 46 Snelgrove DW, Lusztyk J, Banks JT, Mulder P, Ingold KU. J. Am. Chem. Soc. 2001; 123: 469
- 47 Abraham MH, Grellier PL, Prior DV, Morris JJ, Taylor PJ. J. Chem. Soc., Perkin Trans. 2 1990; 521
- 48 Wayner DD. M, Lusztyk J, Pagé D, Ingold KU, Mulder P, Laarhoven LJ. J, Aldrich HS. J. Am. Chem. Soc. 1995; 117: 8131
- 49a Valgimigli L, Banks JT, Lusztyk J, Ingold KU. J. Org. Chem. 1999; 64: 3381
- 49b Jha M, Pratt DA. Chem. Commun. 2008; 1252
- 49c Avila DV, Ingold KU, Lusztyk J, Green WH, Procopio DR. J. Am. Chem. Soc. 1995; 117: 2929
- 49d Galian RE, Litwinienko G, Pérez-Prieto J, Ingold KU. J. Am. Chem. Soc. 2007; 129: 9280
- 50 Bietti M, Salamone M, DiLabio GA, Jockusch S, Turro NJ. J. Org. Chem. 2012; 77: 1267
- 51 Salamone M, Giammarioli I, Bietti M. Chem. Sci. 2013; 4: 3255
- 52 Nova A, Balcells D. Chem. Commun. 2014; 50: 614
For example, see: