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Cited by 203Advanced Polymer Synthesis and CharacterizationRadical Photochemical ReactionsSulfur-Based Synthesis Techniques

Fun with radicals: Some new perspectives for organic synthesis

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Quiclet-Sire, Béatrice, Zard, Samir Z.·2010·Pure and Applied Chemistry
DOI 10.1351/pac-con-10-08-07
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Abstract

The degenerative radical addition-transfer of xanthates onto alkenes allows the rapid assembly of richly functionalized structures. Various families of open-chain, cyclic, and polycyclic compounds can thus be readily accessed. Furthermore, the process can be extended to the synthesis or modification of aromatic and heteroaromatic derivatives by exploiting the possibility of using peroxides both as initiators and stoichiometric oxidants. The modification of existing polymers and the controlled synthesis of block polymers by what is now known as the RAFT/MADIX (reversible addition–fragmentation transfer/macromolecular design by interchange of xanthate) process is described briefly.

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  • β-Scission of the intermediate radical formed upon radical addition to the sulfur atom of the C=S double bond plays a vital role in reactions such as the Barton-McCombie reaction and RAFT polymerization.

    “In these reactions, β-scission of the intermediate radical formed upon radical addition to the sulfur atom of the C=S double bond plays a vital role (Figure 1A).”

    From Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones (2023) · cites this paper as [4]

    The 'Degenerative transfer of xanthates and related groups' section (p. 520) describes radical addition to a thiocarbonyl group followed by β-scission of an intermediate radical. 'Applications to polymer chemistry' says RAFT uses this addition–fragmentation mechanism, and 'Conclusion and perspectives' (p. 547) connects the general mechanism to Barton–McCombie deoxygenation. The passages do not support the more specific assertion that the radical adds to the sulfur atom of C=S. (LLM, conf=0.84)

    Experimental — accuracy not yet measured

  • Thiocarbonyl compounds are fundamentally useful in radical chemistry and are extensively utilized to produce various molecules and macromolecules in reactions such as the Barton-McCombie reaction and RAFT polymerization.

    “Thiocarbonyl compounds are fundamentally useful in radical chemistry and are extensively utilized to produce various molecules and macromolecules in reactions such as the Barton–McCombie reaction and reversible addition–fragmentation chain transfer (RAFT) polymerization.1−4”

    From Direct Radical Copolymerizations of Thioamides To Generate Vinyl Polymers with Degradable Thioether Bonds in the Backbones (2023) · cites this paper as [4]

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Research works printed but not linked: 114

  1. For recent books on radicals in synthesis, see: (a) P. Renaud, M. P. Sibi (Eds.). Radicals in Organic Synthesis, Vols. 1 and 2, Wiley-VCH, Weinheim (2001);
  2. S. Z. Zard. Radicals Reactions in Organic Synthesis, Oxford University Press, Oxford (2003).
  3. a) S. Z. Zard. Org. Biomol. Chem. 5, 205 (2007);
  4. S. Z. Zard. Aust. J. Chem. 59, 663 (2006);
  5. B. Quiclet-Sire, S. Z. Zard. Chem.-Eur. J. 12, 6002 (2006);
  6. B. Quiclet-Sire, S. Z. Zard. Top. Curr. Chem. 264, 201 (2006);
  7. S. Z. Zard. In Radicals in Organic Synthesis, Vol. 1, P. Renaud, M. P. Sibi (Eds.), pp. 90-108, Wiley-VCH, Weinheim (2001);
  8. B. Quiclet-Sire, S. Z. Zard. Phosphorus, Sulfur, Silicon 153-154, 137 (1999);
  9. B. Quiclet-Sire, S. Z. Zard. J. Chin. Chem. Soc. 46, 139 (1999);
  10. S. Z. Zard. Angew. Chem., Int. Ed. Engl. 36, 672 (1997).
  11. M. Destarac, X. Franck, D. Charmot, S. Z. Zard. Macromol. Rapid Commun. 21, 1035 (2000).
  12. A. Liard, B. Quiclet-Sire, S. Z. Zard. Tetrahedron Lett. 37, 5877 (1996).
  13. a) D. H. R. Barton, D. O. Jang, J. Cs. Jaszberenyi. Tetrahedron Lett. 33, 5709 (1992);
  14. J. Boivin, R. Jrad, S. Jugé, V. T. Nguyen. Org. Lett. 5, 1645 (2003).
  15. a) M. Heinrich, S. Z. Zard. Org. Lett. 6, 4969 (2004);
  16. P. Boutillier, B. Quiclet-Sire, S. N. Zafar, S. Z. Zard. Tetrahedron: Asymmetry 21, 1649 (2010).
  17. a) C. Mougin, J. Sançon, S. Z. Zard. Heterocycles 74, 211 (2007);
  18. J. A. Wilkinson, N. Ardes- Guisot, S. Duckia, J. Leonard. Tetrahedron Lett. 46, 8053 (2005).
  19. O. Bergeot, C. Corsi, M. El Qacemi, S. Z. Zard. Org. Biomol. Chem. 4, 278 (2006).
  20. M. Corbet, M. de Greef, S. Z. Zard. Org. Lett. 10, 253 (2008).
  21. a) M. de Greef, S. Z. Zard. Tetrahedron 60, 7781 (2004);
  22. S. K. Bagal, M. de Greef, S. Z. Zard. Org. Lett. 8, 147 (2006).
  23. a) S. Ahmed, L. A. Baker, R. S. Grainger, P. Innocenti, C. E. Quevedo. J. Org. Chem. 73, 8116 (2008);
  24. R. S. Grainger, P. Innocenti. Heteroat. Chem. 18, 568 (2007);
  25. R. S. Grainger, E. J. Welsh. Angew. Chem., Int. Ed. 46, 5377 (2007);
  26. R. S. Grainger, P. Innocenti. Angew. Chem., Int. Ed. 43, 3445 (2004);
  27. G. Lopez-Valdez, S. Olguın-Uribe, L. D. Miranda. Tetrahedron Lett. 48, 8285 (2007);
  28. M. L. Coote, C. J. Easton, S. Z. Zard. J. Org. Chem. 71, 4996 (2006);
  29. J. E. Forbes, R. N. Saicic, S. Z. Zard. Tetrahedron 55, 3791 (1999);
  30. J. E. Forbes, S. Z. Zard. Tetrahedron 49, 8257 (1993);
  31. J. E. Forbes, S. Z. Zard. J. Am. Chem. Soc. 112, 2034 (1990);
  32. J. E. Forbes, S. Z. Zard. Tetrahedron Lett. 30, 4367 (1989);
  33. a) F. Gagosz, S. Z. Zard. Org. Synth. 84, 32 (2007);
  34. L. Tournier, S. Z. Zard. Tetrahedron Lett. 46, 455 (2005);
  35. F. Gagosz, S. Z. Zard. Org. Lett. 5, 2655 (2003);
  36. F. Bertrand, V. Pevere, B. Quiclet-Sire, S. Z. Zard. Org. Lett. 3, 1069 (2001);
  37. T. Biadatti, B. Quiclet- Sire, J.-B. Saunier, S. Z. Zard. Tetrahedron Lett. 39, 19 (1998).
  38. a) B. Quiclet-Sire, S. Z. Zard. Org. Lett. 10, 3279 (2008);
  39. B. Quiclet-Sire, G. Revol, S. Z. Zard. Org. Lett. 11, 3554 (2009).
  40. B. Quiclet-Sire, G. Revol, S. Z. Zard. Tetrahedron 66, 6656 (2010).
  41. B. Quiclet-Sire, S. Z. Zard. Heterocycles (2010). In press.
  42. F. Lebreux, B. Quiclet-Sire, S. Z. Zard. Org. Lett. 11, 2844 (2009).
  43. A. Srikrishna. In Radicals in Organic Synthesis, Vol. 2, P. Renaud, M. P. Sibi (Eds.), pp. 151-187, Wiley-VCH, Weinheim (2001).
  44. E. Bacqué, F. Pautrat, S. Z. Zard. Org. Lett. 5, 325 (2003).
  45. G. Binot, S. Z. Zard. Tetrahedron Lett. 44, 7703 (2003).
  46. R. Heng, B. Quiclet-Sire, S. Z. Zard. Tetrahedron Lett. 50, 3613 (2009).
  47. M. E. Briggs, M. El Qacemi, C. Kalai, S. Z. Zard. Tetrahedron Lett. 45, 6017 (2004).
  48. a) C. Alameda-Angulo, B. Quiclet-Sire, S. Z. Zard. Tetrahedron Lett. 47, 913 (2006);
  49. M.-P. Denieul, B. Quiclet-Sire, S. Z. Zard. Tetrahedron Lett. 37, 5495 (1996).
  50. M. de Greef, S. Z. Zard. Org. Lett. 9, 1773 (2007).
  51. M. El Qacemi. Ph.D. Thesis, Ecole Polytechnique, Palaiseau (2005).
  52. B. Quiclet-Sire, T. Tétart, S. Z. Zard. Unpublished observations. 33. (a) A. Gheorghe, B. Quiclet-Sire, X. Vila, S. Z. Zard. Tetrahedron 63, 7187 (2007);
  53. A. Gheorghe, B. Quiclet-Sire, X. Vila, S. Z. Zard. Org. Lett. 7, 1653 (2005);
  54. B. Quiclet-Sire, G. Revol, S. Z. Zard. Org. Lett. 11, 2832 (2009).
  55. F. Gagosz, S. Z. Zard. Org. Lett. 4, 4345 (2002).
  56. B. Sortais. Ph.D. Thesis, Ecole Polytechnique, Palaiseau (2002).
  57. a) N. Charrier. Ph.D. Thesis. Ecole Polytechnique, Palaiseau (2008); see also: (b)
  58. T. Kaoudi, B. Quiclet-Sire, S. Seguin, S. Z. Zard. Angew. Chem., Int. Ed. 39, 731 (2000).
  59. L. Petit, S. Z. Zard. Chem. Commun. 46, 5148 (2010).
  60. A. Cordero Vargas, B. Quiclet-Sire, S. Z. Zard. Org. Lett. 5, 3717 (2003).
  61. a) E. Bacqué, M. El Qacemi, S. Z. Zard. Org. Lett. 6, 3671 (2004);
  62. M. El Qacemi. Ph.D. Thesis, Ecole Polytechnique, Palaiseau (2005).
  63. a) R. Yamasaki, A. Tanatani, I. Azumaya, S. Saito, K. Yamaguchi, H. Kagechika. Org. Lett. 5, 1265 (2003) and refs. cited therein;
  64. O. M. Musa, J. Horner, M. Newcomb. J. Org. Chem. 64, 1022 (1999);
  65. G. Stork, R. Mah. Heterocycles 28, 723 (1989); see also: (d)
  66. G. Binot, S. Z. Zard. Tetrahedron Lett. 46, 7503 (2005);
  67. Y. Laot, L. Petit, S. Z. Zard. Chem. Commun. 46, 5784 (2010).
  68. A. Biéchy, S. Z. Zard. Org. Lett. 11, 2800 (2009).
  69. J. Magolan, C. A. Carson, M. A. Kerr. Org. Lett. 10, 1437 (2008).
  70. For earlier examples of intermolecular additions of xanthates to herteraromatics, see: (a) P. E. Reyes-Gutierrez, R. O. Torres-Ochoa, R. Martınez, L. D. Miranda. Org. Biomol. Chem. 7, 1388 (2009);
  71. O. Guadarrama-Morales, F. Mendez, L. D. Miranda. Tetrahedron Lett. 48, 4515 (2007);
  72. F. Coppa, F. Fontana, F. Minisci, G. Pianese, P. Tortoreto, L. Zhao. Tetrahedron Lett. 33, 687 (1992).
  73. F. Bertrand, B. Quiclet-Sire, S. Z. Zard. Angew. Chem., Int. Ed. 38, 1943 (1999).
  74. Z. Li, S. Z. Zard. Org. Lett. 11, 2868 (2009).
  75. Z. Li, S. Z. Zard. Tetrahedron Lett. 50, 6973 (2009).
  76. a) For a review, see: F. Bertrand, F. Le Guyader, L. Liguori, G. Ouvry, B. Quiclet-Sire, S. Seguin, S. Z. Zard. C. R. Acad. Sci. Paris II4, 547 (2000);
  77. N. Charrier, S. Z. Zard. Angew. Chem., Int. Ed. 47, 9443 (2008);
  78. F. Le Guyader, B. Quiclet-Sire, S. Seguin, S. Z. Zard. J. Am. Chem. Soc. 119, 7410 (1997);
  79. M. F. Semmelhack, L. Wu, R. A. Pascal Jr., D. M. Ho. J. Am. Chem. Soc. 125, 10496 (2003);
  80. B. Quiclet-Sire, S. Seguin, S. Z. Zard. Angew. Chem., Int. Ed. 37, 2864 (1998);
  81. S. Kim, S. Kim. Bull. Chem. Soc. Jpn. 80, 809 (2007);
  82. J. Y. Lee, S. Kim. Bull. Korean Chem. Soc. 27, 189 (2006);
  83. S. Kim. Adv. Synth. Catal. 346, 19 (2004);
  84. S. Kim, C. J. Lim. Angew. Chem., Int. Ed. 41, 3265 (2002);
  85. S. Kim, H.-J. Song, T.-L. Choi, J.-Y. Yoon. Angew. Chem., Int. Ed. 40, 2524 (2001);
  86. S. Cren, P. Schär, P. Renaud, K. Schenk. J. Org. Chem. 74, 2942 (2009);
  87. L. Chabaud, Y. Landais, P. Renaud. Org. Lett. 7, 2587 (2005);
  88. L. Chabaud, Y. Landais, P. Renaud. Org. Lett. 4, 4257 (2002);
  89. P. Panchaud, P. Renaud. J. Org. Chem. 69, 3205 (2004);
  90. P. Panchaud, C. Ollivier, P. Renaud, S. Zigmantas. J. Org. Chem. 69, 2755 (2004);
  91. C. Ollivier, P. Renaud. J. Am. Chem. Soc. 123, 4717 (2001);
  92. C. Ollivier, P. Renaud. J. Am. Chem. Soc. 122, 6496 (2000).
  93. a) H. Fliri, C. P. Mak. J. Org. Chem. 50, 3438 (1985);
  94. G. Ouvry, B. Quiclet-Sire, S. Z. Zard. Angew. Chem., Int. Ed. 45, 5002 (2006);
  95. N. Charrier, D. Gravestock, S. Z. Zard. Angew. Chem., Int. Ed. 45, 6520 (2006).
  96. a) N. Charrier, B. Quiclet-Sire, S. Z. Zard. J. Am. Chem. Soc. 130, 8898 (2008);
  97. W. Kosnik, M. Michalak, B. Quiclet-Sire, S. Z. Zard. Unpublished observations. 53. A handbook on the RAFT/MADIX technology has recently appeared: (a) C. Barner-Kowollik (Ed.). Handbook of RAFT Polymerization, Wiley-VCH, Weinheim (2008); for other reviews, see: (b)
  98. G. Moad, E. Rizzardo, S. H. Thang. Aust. J. Chem. 62, 1402 (2009);
  99. G. Moad, E. Rizzardo, S. H. Thang. Aust. J. Chem. 58, 379 (2005);
  100. S. Perrier, T. Takolpuckdee. J. Polym. Sci., Part A: Polym. Chem. 43, 5347 (2005); for the original patents on MADIX and RAFT, see: (e)
  101. P. Corpart, D. Charmot, T. Biadatti, S. Z. Zard, D. Michelet. WO 9858974 (1998) [Chem. Abstr., 130, 82018 (1999)];
  102. T. P. Le, G. Moad, E. Rizzardo, S. H. Thang. Int. Pat. 9801478 [Chem. Abstr. 128, 115390 (1998)].
  103. a) B. Quiclet-Sire, S. Z. Zard. Bull. Korean Chem. Soc. 31, 543 (2010);
  104. G. Bouhadir, N. Legrand, B. Quiclet-Sire, S. Z. Zard. Tetrahedron Lett. 40, 277 (1999).
  105. M. Corbet, Z. Ferjancic, B. Quiclet-Sire, S. Z. Zard. Org. Lett. 10, 3579 (2008).
  106. a) E. Bacqué, M. El Qacemi, S. Z. Zard. Org. Lett. 7, 3817 (2005);
  107. L. Boiteau, J. Boivin, B. Quiclet-Sire, J.-B. Saunier, S. Z. Zard. Tetrahedron 54, 2087 (1998);
  108. Y. Laot, L. Petit, S. Z. Zard. Org. Lett. 12, 3426 (2010).
  109. D. H. R. Barton, S. W. McCombie. J. Chem. Soc., Perkin Trans. 1 1574 (1975).
  110. a) A.-C. Callier-Dublanchet, B. Quiclet-Sire, S. Z. Zard. Tetrahedron Lett. 36, 8791 (1995);
  111. M.-H. Le Tadic-Biadatti, A.-C. Callier-Dublanchet, J. H. Horner, B. Quiclet-Sire, S. Z. Zard, M. Newcomb. J. Org. Chem. 62, 559 (1997);
  112. A.-C. Callier-Dublanchet, B. Quiclet-Sire, S. Z. Zard. Tetrahedron Lett. 38, 2463 (1997); for a recent review on nitrogen-centered radicals, see: (d) S. Z. Zard. Chem. Soc. Rev. 37, 1603 (2008).
  113. a) A. Biéchy, S. Hachisu, B. Quiclet-Sire, L. Ricard, S. Z. Zard. Angew. Chem., Int. Ed. 47, 1436 (2008);
  114. A. Biéchy, S. Hachisu, B. Quiclet-Sire, L. Ricard, S. Z. Zard. Tetrahedron 65, 6730 (2009).

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Authors
Quiclet-Sire, B., & Zard, S. Z.
Affiliations
  • 1Organic Synthesis Laboratory, CNRS UMR 7652, Ecole Polytechnique, 91128, Palaiseau, France
  • Centre National de la Recherche Scientifique (FR)
ORCID
Zard, Samir Z.
Venue
Pure and Applied Chemistry
Publisher
Walter de Gruyter GmbH
Published
2010-10-15
Volume
83
Issue
3
Pages
519-551
ISSN
  • 0033-4545 (ISSN-L)
  • 1365-3075
DOI
10.1351/pac-con-10-08-07
OpenAlex
W2117324828
Cited by
199
References
8
Citations by year
2025: 2 · 2024: 7 · 2023: 12 · 2022: 12 · 2021: 17 · 2020: 10 · 2019: 18 · 2018: 19 · 2017: 10 · 2016: 19 · 2015: 15 · 2014: 16 · 2013: 13 · 2012: 16
FWCI
6.50
Type
journal article
Language
en
Open access
Licence
other-oa
Locations
  • Pure and Applied Chemistry (publishedVersion, other-oa)
  • HAL (submittedVersion, other-oa)
Topics
  • Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
  • Physical Sciences › Chemistry › Organic Chemistry › Radical Photochemical Reactions
  • Physical Sciences › Chemistry › Organic Chemistry › Sulfur-Based Synthesis Techniques
Keywords
xanthates, alkenes, radical polymerization, peroxide initiators, aromatic compounds, heteroarenes, polymer modification, RAFT, MADIX

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