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Electrophilic Molecular Rearrangements

  • T. S. Stevens

Abstract

An electrophilic molecular rearrangement is one in which the migrating radical leaves an electron pair on the atom of departure (migration origin) and becomes linked through an electron pair on the destination atom (migration terminus). An early example is the thermal isomerization of isocyanides to nitriles1:

Keywords

Quaternary Ammonium Salt Anionic Carbon Amine Oxide Molecular Rearrangement Thermal Rearrangement 
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References

  1. 1.
    Weith, W.: ‘Beziehungen zwischen aromatischen Senfölen und Cyanüren’, Ber. dtsch. chem. Ges., 6 (1873) 210–214CrossRefGoogle Scholar
  2. 2.
    Stevens, T. S., Creighton, E. M., Gordon, A. B. and Macnicol, M.: ‘Degradation of Quaternary Ammonium Salts. I’, J. chem. Soc. (1928) 3193–3197Google Scholar
  3. 3.
    Thomson, T. and Stevens, T. S.: ‘Degradation of Quaternary Ammonium Salts. IV’, J. chem. Soc. (1932) 55–69Google Scholar
  4. 4.
    Thomson, T. and Stevens, T. S.: ‘Degradation of Quaternary Ammonium Salts. Vii’, J. chem. Soc. (1932) 1932–1940Google Scholar
  5. 5.
    Dunn, J. L. and Stevens, T. S.: ‘Degradation of Quaternary Ammonium Salts. VI’, J. chem. Soc. (1932) 1926–1931Google Scholar
  6. 6.
    Johnstone, R. A. W. and Stevens, T. S.: ‘Degradation of Quaternary Ammonium Salts. IX’, J. chem. Soc. (1955) 4487–4488Google Scholar
  7. 7.
    Campbell, A., Houston, A. H. J. and Kenyon, J.: ‘The rearrangement of 1-phenacyl-a-phenylethyldimethylammonium Bromide’, J. chem. Soc. (1947) 93–95;Google Scholar
  8. Brewster, J. H. and Kline, M. W.: ‘Nucleophilic Displacement via Frontal Attack’, J. Amer. chem. Soc. 74 (1952) 5179–5182CrossRefGoogle Scholar
  9. 8.
    Millard, B. J. and Stevens, T. S.: ‘Electrophilic Rearrangements’, J. chem. Soc. (1963) 3397–3403Google Scholar
  10. 9.
    Wittig, G., Tenhaeff, H., Schoch, W. and Koenig, G.: ‘Einige Synthesen über Ylide’, Liebigs Ann. 572 (1951) 1–22Google Scholar
  11. 10.
    Hughes, E. D. and Ingold, C. K.: ‘Influence of Poles and Polar Linkings on the Course Pursued by Elimination Reactions. Xiii’, J. chem. Soc. (1933) 69–75Google Scholar
  12. 11.
    Sommelet, M.: ‘Sur un mode particulier de réarrangement intramoléculaire’, C.R. Acad. Sci., Paris, 205 (1937) 56–58Google Scholar
  13. 12.
    Wittig, G., Mangold, R. and Felletschin, G.: ‘Über die Stevens’sche und Sommelet’sche Umlagerung als Ylid-Reaktionen’, Liebigs Ann. 560 (1948) 116–127Google Scholar
  14. 13.
    Kantor, S. W. and Hauser, C. R.: ‘Rearrangements of Benzyltrimethyl- Ammonium Ion Involving Migration into the Ring’, J. Amer. chem. Soc. 73 (1951) 4122–4131CrossRefGoogle Scholar
  15. 14.
    Zimmermann, H. E. In Molecular Rearrangements (P. de Mayo, Ed.) 1st edn, Interscience, New York & London, 1963Google Scholar
  16. 15.
    Wittig, G. and Felletschin, G.: ‘Über Fluorenylide und die Stevenssche Umlagerung’, Liebigs Ann. 555 (1944) 133–145Google Scholar
  17. 16.
    Puterbaugh, W. H. and Hauser, C. R.: ‘Isolation of Intermediate Alkali Salt in Rearrangement of Benzyltrimethylammonium Ion’, J. Amer. chem. Soc. 86 (1964) 1105–1107CrossRefGoogle Scholar
  18. 17.
    Hauser, C. R. and Van Eenam, D. N.: ‘Rearrangement to form an exo- Methylenecyclohexadieneamine’, J. Amer. chem. Soc. 79 (1957) 5512–5520CrossRefGoogle Scholar
  19. Hauser, C. R. and Van Eenam, D. N.: ‘Rearrangement to form an exo- Methylenecyclohexadieneamine’, J. Amer. chem. Soc. 79 (1957) 5520–5524;CrossRefGoogle Scholar
  20. Hauser, C. R. and Van Eenam, D. N.: ‘Rearrangements of 2,6-Dimethyl-and 2,3,4,6-Tetramethylbenzyltrimethylammonium Ions’, J. org. Chem. 23 (1958) 865–869CrossRefGoogle Scholar
  21. 18.
    Wittig, G. and Streib, H.: ‘Zur Erschliessung der Isoindole’, Liebigs Ann. 584 (1953) 1–22Google Scholar
  22. 19.
    Bumgardner, C. L.: ‘Sommelet—Hauser Rearrangement of Allylbenzyldimethylammonium Bromide and Cyclopropylcarbinylbenzyldimethylammonium Bromide’, J. Amer. chem. Soc. 85 (1963) 73–78CrossRefGoogle Scholar
  23. 20.
    Lednicer, D. and Hauser, C. R.: ‘A Novel Ring Enlargement Using Sodium Amide’, J. Amer. chem. Soc. 79 (1957) 4449–4451;CrossRefGoogle Scholar
  24. Jones, G. C. and Hauser, C. R.: ‘Rearrangement of 1,1-Dimethyl-2-phenylpyrrolidinium Ion’, J. org. Chem. 27 (1962) 3572–3576;CrossRefGoogle Scholar
  25. Daniel, H. and Weygand, F.: ‘Die Fragmentierung substituierter Pyrrolidiniumverbindungen mit Phenyl-lithium’, Liebigs Ann. 671 (1964) 111–118Google Scholar
  26. 21.
    Kohlmeier, G. and Rabinovitch, B. S.: ‘Kinetics of Thermal Isomerization of p-Tolyl Isocyanide’, J. phys. Chem. 63 (1959) 1793–1794;Google Scholar
  27. Schneider, F. W. and Rabinovitch, B. S.: ‘The Thermal Unimolecular Isomerization of Methyl Isocyanide’, J. Amer. chem. Soc. 84 (1962) 4215–4230;CrossRefGoogle Scholar
  28. Schneider, F. W. and Rabinovitch, B. S.: ‘The Unimolecular Isomerization of Methyl-d3-Isocyanide’, J. Amer. chem. Soc. 85 (1963) 2365–2370;CrossRefGoogle Scholar
  29. Rabinovitch, B. S., Gilderson, P. W. and Schneider, F. W.: ‘The Thermal Unimolecular Isomerization of Methyl-d1-Isocyanide’, J. Amer. chem. Soc. 87 (1965) 158–160CrossRefGoogle Scholar
  30. 22.
    Wittig, G. and Laib, H.: ‘Zur Stevensschen Umlagerung von Oniumsalzen’, Liebigs Ann. 580 (1953) 57–68Google Scholar
  31. 23.
    Thomson, T. and Stevens, T. S.: ‘Molecular Rearrangement in Sulphur Compounds’, J. chem. Soc. (1932) 69–73;Google Scholar
  32. Böhme, H. and Krause, W. Über Dialkyl-phenacyl-sulfoniumsalze und ihre Spaltung mit wässrigen Laugen’, Chem. Ber. 82 (1949) 426–432;CrossRefGoogle Scholar
  33. Ruiz, E. B.: ‘Reexamination and Mechanism of the Rearrangement of Methylbenzylphenacylsulfonium Hydroxide in weakly alkaline solution’, Chem. Abstr. 54 (1960) 7623hGoogle Scholar
  34. 24.
    Pinck, L. A. and Hilbert, G. E.: ‘Molecular Rearrangement of Fluorylidene Dimethyl Sulfide to Fluorene-l-dimethyl Sulfide’, J. Amer. chem. Soc. 68 (1946) 751–753CrossRefGoogle Scholar
  35. 25.
    Pascual Teresa, J. DE and Sanchez Bellido, H.: ‘Molecular Rearrangement of Sulfonium Compounds, II, III’, Chem. Abstr. 51 (1957) 6537Google Scholar
  36. 26.
    Schorigin, P.: ‘Über die Umlagerungen von Benzyläthern, I, II’, Ber. dtsch. chem. Ges. 57 (1924) 1634–1637;CrossRefGoogle Scholar
  37. Schorigin, P.: ‘Über die Umlagerungen von Benzyläthern, I, II’, Ber. dtsch. chem. Ges. 58 (1925) 2028–2036;CrossRefGoogle Scholar
  38. Schorigin, P.: ‘Weitere Versuche über die Umsetzungen von Äthern mit metallischem Natrium’, Ber. dtsch. chem. Ges. 59 (1926) 2510–2514CrossRefGoogle Scholar
  39. 27.
    Schlenk, W. and Bergmann, E.: ‘Einige Spaltungsreaktionen mittels Alkalimetallen’, Liebigs Ann. 464 (1928) 35–42Google Scholar
  40. 28.
    Wittig, G., Döser, H. and Lorenz, I.: ‘Über die Isomerisierbarkeit metallierter Fluorenyläther’, Liebigs Ann. 562 (1949) 192–205Google Scholar
  41. 29.
    Cast, J., Stevens, T. S. and Holmes, J.: ‘Molecular Rearrangement and Fission of Ethers by Alkaline Reagents’, J. chem. Soc. (1960) 3521–3527Google Scholar
  42. 30.
    Wittig, G. and Löhmann, L.: ‘Über die kationotrope Isomerisation gewisser Benzyläther’, Liebigs Ann. 550 (1942) 260–268Google Scholar
  43. 31.
    Schöllkopf, U. and Eisert, M.: ‘α-Eliminierung bei alkalimetallorganischen Verbindungen’, Liebigs Ann. 664 (1963) 76–88Google Scholar
  44. 32.
    Hauser, C. R. and Kantor, S. W.: ‘Rearrangement of Benzyl Ethers to Carbinols by Potassium Amide’, J. Amer. chem. Soc. 73 (1951) 1437–1441CrossRefGoogle Scholar
  45. 33.
    Curtin, D. Y. and Leskowitz, S.: ‘Cleavage and Rearrangement of Ethers with Base. II’, J. Amer. chem. Soc. 73 (1951) 2633–2636CrossRefGoogle Scholar
  46. 31.
    Curtin, D. Y. and Proofs, W. R.: ‘Cleavage and Rearrangement of Ethers with Base. III’, J. Amer. chem. Soc. 76 (1954) 494–499CrossRefGoogle Scholar
  47. 35.
    Wittig, G. and Happe, W.: ‘Über den Einfluss der metallorganischen Bindung auf die Isomerisierbarkeit metallierter Äther’, Liebigs Ann. 557 (1947) 205–220Google Scholar
  48. 36.
    Wittig, G. and Stahnecker, E.: ‘Zum Chemismus der Umlagerung von metallierten Benzhydryl-Phenyläthern’, Liebigs Ann. 605 (1957) 69–93Google Scholar
  49. 37.
    Dahn, H. and Souls, U.: ‘Über eine Umlagerung tertiärer Amine durch Lithiumaluminiumhydrid’, Hely. chim. acta. 34 (1951) 907–915CrossRefGoogle Scholar
  50. 38.
    Cockburn, W. F., Johnstone, R. A. W. and Stevens, T. S.: ‘Molecular Rearrangement of Tertiary Amines I’, J. chem. Soc. (1960) 3340–3346;Google Scholar
  51. Johnstone, R. A. W. and Stevens, T. S.: ‘Molecular Rearrangement of Tertiary Amines. II’, J. chem. Soc. (1960) 3346–3350Google Scholar
  52. 39.
    Curtin, D. Y. and Leskowitz, S.: ‘Cleavage and Rearrangement of Ethers with Bases. I’, J. Amer. chem. Soc. 73 (1951) 2630–2633CrossRefGoogle Scholar
  53. 40.
    Schöllkopf, U. and Fabian, W.: ‘Umlagerungen organischer Anionen. I’, Liebigs Ann. 642 (1961) 1–21Google Scholar
  54. 41.
    Jenny, E. F. and Druey, J.: ‘On the Mechanism of the Stevens Rearrangement’ Angew. Chem., Int. edn, 1 (1962) 155–156;CrossRefGoogle Scholar
  55. Lansbury, P. T. and Pattison, V. A.: ‘Some Reactions of a-Metalated Ethers’, J. org. Chem. 27 (1962) 1933–1939;CrossRefGoogle Scholar
  56. Jenny, E. F. and Schenker, K.: ‘The Mechanism of Anionic Rearrangements—A Stevens-1,3-Rearrangement’, Angew. Chem. (Int. edn.) 4 (1965) 441–442Google Scholar
  57. 42.
    Wittig, G. and Clausnizer, R.: ‘Zum Chemismus der intraionischen Ätherisomerisation’, Liebigs Ann. 588 (1954) 145–166Google Scholar
  58. 43.
    Hauser, C. R., Kantor, S. W. and Brasen, W. R.: ‘Rearrangement of Benzyl Sulfides to Mercaptans and of Sulfonium Ions to Sulfides Involving the Aromatic Nucleus by Alkali Amides’, J. Amer. chem. Soc. 75 (1953) 2660–2663CrossRefGoogle Scholar
  59. 44.
    Hellmann, H. and Eberle, D.: ‘Umsetzungen von Thioäthern mit o-Fluorophenylmagnesiumbromid’, Liebigs Ann. 662 (1963) 188–201Google Scholar
  60. 45.
    Grovenstein, E.: ‘Preparation of 2-Chloro-1,1,1-triphenylethane and Rearrangement in its Reaction with Sodium’, J. Amer. chem. Soc. 79 (1957) 4985–4990;CrossRefGoogle Scholar
  61. Grovenstein, E. and Williams, L. P.: ‘Rearrangement in the Reaction of 2-Chloro-1,1,1-triphenylethane with Lithium and Potassium’, J. Amer. chem. Soc. 83 (1961) 412–416;CrossRefGoogle Scholar
  62. Grovenstein, E. and Williams, L. P.: ‘Rearrangement in the Reaction of 1-Chloro-2,2,3-triphenylpropane with Lithium’, J. Amer. chem. Soc. 83 (1961) 2537–2541;CrossRefGoogle Scholar
  63. Zimmermann, H. E. and Smentowski, A. F. J.: ‘Carbanion Rearrangements. I’, J. Amer. chem. Soc. 79 (1957) 5455–5457;CrossRefGoogle Scholar
  64. Zimmermann, H. E. and Zweig, A.: ‘Carbanion Rearrangements. II’, J. Amer. chem. Soc. 83 (1961) 1196–1213CrossRefGoogle Scholar
  65. 46.
    Ash, A. S. F., Challenger, F. and Greenwood, D. The Isomerisation of Diallyesulphilimines. I’, J. chem. Soc. (1951) 1877–1882;Google Scholar
  66. Ash, A. S. F. and Challenger, F.: ‘The Isomerisation of Diallyesulphilimines. II’, J. chem. Soc. (1952) 2792–2796Google Scholar
  67. 47.
    Meisenheimer, J.: ‘Ober eine eigenartige Umlagerung des Methyl-allylanilin-N-oxyds’, Ber. dtsch. chem. Ges. 52 (1919) 1667–1677;CrossRefGoogle Scholar
  68. Meisenheimer, J., Greeske, H. and Willmersdorf, A.: ‘Ober das Verhalten von Allylund Benzyl-amin-oxyden gegen Natronlauge’, Ber. dtsch. chem. Ges. 55 (1922) 513–522CrossRefGoogle Scholar
  69. 48.
    Kleinschmidt, R. F. and Cope, A. C.: ‘Rearrangement of Allyl Groups in Amine Oxides’, J. Amer. chem. Soc. 66 (1944) 1929–1933;CrossRefGoogle Scholar
  70. Cope, A. C. and Towle, P. H.: ‘Rearrangement of Allyldialkylamine Oxides and Benzyldimethylamine Oxide’, J. Amer. chem. Soc. 71 (1949) 3423–3428;CrossRefGoogle Scholar
  71. Cope, A. C., Foster, T. T. and Towle, P. H.: ‘Thermal Decomposition of Amine Oxides to Olefins and Dialkylhydroxylamines’, J. Amer. chem. Soc. 71 (1949) 3929–3935CrossRefGoogle Scholar
  72. 49.
    Wragg, A. H., Stevens, T. S. and Ostle, D. M.: ‘The Rearrangement of Amine Oxides’, J. chem. Soc. (1958) 4057–4064Google Scholar
  73. 50.
    Cope, A. C. and Haven, A. C.: ‘Rearrangement of Oxime N-Ethers’, J. Amer. chem. Soc. 72 (1950) 4896–4903CrossRefGoogle Scholar
  74. 51.
    Arbusov, A. E.: ‘The Conversion of Tervalent into Quinquevalent Derivatives of Phosphorus’, J. chem. Soc. (Abstracts) 92 (1907) 275–276Google Scholar
  75. 52.
    Wragg, A. H., Mcfadyen, J. S. and Stevens, T. S.: ‘The Rearrangement of Sulphinic Esters’, J. chem. Soc. (1958) 3603–3605Google Scholar
  76. 53.
    Bunnett, J. F. and Zahler, R. E.: ‘Nucleophilic Substitution Reactions: The Smiles Rearrangement’, Chem. Rev. 49 (1951) 362–372;Google Scholar
  77. Warren, L. A. and Smiles, S.: ‘The Rearrangement of Hydroxy-sulphones. I, II’, J. chem. Soc. (1931) 2207–2211; (1932) 1040–1047;Google Scholar
  78. Galbraith, F. and Smiles, S.: ‘The Rearrangement of Hydroxy-sulphones. V’, J. chem. Soc. (1935) 1234–1238;Google Scholar
  79. Evans, W. J. and Smiles, S.: ‘A Rearrangement of o-Acetamido-sulphones and -sulphides’, J. chem. Soc. (1935) 181–188Google Scholar
  80. 54a.
    Bunnett, J. F. and Okamoto, T.: ‘Steric Acceleration: The Smiles Rearrangement’, J. Amer. chem. Soc. 78 (1956) 5363–5367CrossRefGoogle Scholar
  81. 54b.
    Chapman, D. D., Jones, E. T., Wilgus, H. S., Nelander, D. H. and Gates, J. W.: ‘The Chemistry of Thioethersubstituted Hydroquinones and Quinones. III’, J. org. Chem., 30 (1965) 1520–1523CrossRefGoogle Scholar
  82. 55.
    Coats, R. R. and Gibson, D. T.: ‘The Reversibiity of the Rearrangement of o-Hydroxy-sulphones’, J. chem. Soc. (1940) 442–446Google Scholar
  83. 56.
    Roberts, K. C. and DE Worms, C. G. M.: ‘A Rearrangement of o-Aminodiphenyl Ethers. I’, J. chem. Soc. (1934) 727–729Google Scholar
  84. 57.
    Evans, W. J. and Smiles, S.: ‘A Rearrangement of Carbamyl-sulphones and -sulphides’, J. chem. Soc. (1936) 329–331;Google Scholar
  85. Tozer, B. T. and Smiles, S.: ‘A Rearrangement of o-Carbamyl Derivatives of Diphenyl Ether’, J. chem. Soc. (1938) 2052–2056Google Scholar
  86. 58.
    Truce, W. E., Ray, W. J., Norman, O. L. and Eickemeyer, D. B. ‘Rearrangements of Aryl Sulphones. I’, J. Amer. chem. Soc. 80 (1958) 3625–3629;CrossRefGoogle Scholar
  87. Truce, W. E. and Ray, W. J.: ‘Rearrangements of Aryl Sulphones, II, III’,Y. Amer. chem. Soc. 81 (1959) 481–484;CrossRefGoogle Scholar
  88. Truce, W. E. and Ray, W. J.: ‘Rearrangements of Aryl Sulphones, II, III’,Y. Amer. chem. Soc. 81 (1959) 484–487;CrossRefGoogle Scholar
  89. Truce, W. E. and Guy, M. M.: ‘Rearrangements of Aryl Sulphones. IV’, J. org. Chem. 26 (1961) 4331–4336;CrossRefGoogle Scholar
  90. Truce, W. E. and Hampton, D. C.: ‘Rearrangement of Sulphones, J. org. Chem. 28 (1963) 2276–2279CrossRefGoogle Scholar
  91. 59.
    Chapman, A. W.: ‘Imino-aryl Ethers. III, IV, V’, J. chem. Soc. 127 (1925) 1992–1998;CrossRefGoogle Scholar
  92. Chapman, A. W.: ‘Imino-aryl Ethers. III, IV, V’, J. chem. Soc. 127 (1926) 2296–2300;CrossRefGoogle Scholar
  93. Chapman, A. W.: ‘Imino-aryl Ethers. III, IV, V’, J. chem. Soc. 127 (1927) 1743–1751CrossRefGoogle Scholar
  94. 60.
    Chapman, A. W.: ‘Dynamic Isomerism Involving Mobile Hydrocarbon Radicals. I-III’, J. chem. Soc. (1929) 2133–2138;Google Scholar
  95. Chapman, A. W.: ‘Dynamic Isomerism Involving Mobile Hydrocarbon Radicals. I-III’, J. chem. Soc. (1930) 2458–2462;Google Scholar
  96. Chapman, A. W.: ‘Dynamic Isomerism Involving Mobile Hydrocarbon Radicals. I-III’, J. chem. Soc. (1930) 2462–2468;Google Scholar
  97. Chapman, A. W. and Perrott, C. H.: ‘Dynamic Isomerism Involving Mobile Hydrocarbon Radicals. IV’, J. chem. Soc. (1932) 1770–1775Google Scholar
  98. 61.
    Makisumi, Y.: ‘Thermal Rearrangement of Allyl 2-Quinolyl Ethers’, Tetrahedron Letrs. (1964) 2833–2838Google Scholar
  99. 62.
    Soer, J. E. and Stevens, T. S. UnpublishedGoogle Scholar
  100. 63.
    Hellmann, H. and Unseld, W.: ‘Einwirkung von tert. Aminen auf o-Metallierte Arylhalogenide. I, II’, Liebigs Ann. 631 (1960) 82–89, 89–94Google Scholar
  101. 64.
    Hellmann, H. and Scheytt, G. M.: ‘Einwirkung von tert. Aminen auf o-Metallierte Arylhalogenide. IV’, Liebigs Ann. 642 (1961) 22–27Google Scholar
  102. 65.
    Hellmann, H. and Scheytt, G. M.: ‘Umlagerungen von quartären Ammoniumsalzen’, Liebigs Ann. 654 (1962) 39–49Google Scholar
  103. 66.
    Bumgardner, C. L. and Freeman, J. P.: ‘Cyclopropylcarbinyl Anions’, Tetrahedron Letrs. (1964) 737–742Google Scholar
  104. 67.
    Babayan, A. T. and Indjikyan, M. H.: ‘A New Rearrangement-Cleavage Reaction of Quaternary Ammonium Salts’, Tetrahedron. 20 (1964) 1371–1376CrossRefGoogle Scholar
  105. 68.
    Dunn, J. L. and Stevens, T. S.: ‘Degradation of Quaternary Ammonium Salts. Viii’, J. chem. Soc. (1934) 279–282Google Scholar
  106. 69.
    Grob, C. A. and Renk, E.: ‘Untersuchungen in der Chinuclidinreihe, 2. 4-Chinuclidin-carbonsäure’, Hely. chem. Acta. 37 (1954) 1681–1688CrossRefGoogle Scholar
  107. 70.
    Dinan, F. J. and Tieckelmann, H.: ‘Rearrangements of Alkoxypyridine 1-Oxides’, J. org. Chem. 29 (1964) 1650–1652CrossRefGoogle Scholar

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  • T. S. Stevens

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