Advertisement

Abstract

In synthesis it is often desirable to protect a carboxyl function in order to bring about specific reactions elsewhere in the molecule and subsequently to regenerate the original carboxyl group under conditions which do not affect other sensitive groups in the substrate. An elegant example of this principle is shown in the route of formation of 6-aminopenicillamic acid (5) from the intermediate (1) [1, 2] in the general synthesis of penicillins due to Sheehan and Henery-Logan [3]. In practice, as in this example, the carboxyl group is most easily blocked in the form of an ester. Table 5.1, at the end of this Chapter, lists those esters which have been most widely employed or have properties which appear to be most suitable for this task. Open image in new window

Keywords

Malonic Acid Benzyl Ester Tetrahedron Letter Cyclic Anhydride Hexamethylphosphoric Triamide 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    J. C. SHEEHAN and D. A. JOHNSON, J. Amer. Chem. Soc., 76, 158 (1954).Google Scholar
  2. 2.
    J. C. SHEEHAN and D. R. HOFF, J. Amer. Chem. Soc., 79, 237 (1957).Google Scholar
  3. 3.
    J. C. SHEEHAN and K. R. HENERY-LOGAN, J. Amer. Chem. Soc., 84, 2983 (1962).Google Scholar
  4. 4.
    S. R. SandLER and W. KARO, Organic Functional Group Preparations, Academic Press, London and New York, 1968, p. 245.Google Scholar
  5. 5.
    M. F. ANSELL and R. H. GIGG IN RODD’S Chemistry of Carbon Compounds (2nd edition, Editor S. Coffey, Elsevier, London, Amsterdam, New York, 1965), Vol. 1C, p. 92.Google Scholar
  6. 6.
    B. F. ERLANGER and R. M. HALL, J. Amer. Chem. Soc., 76, 5781 (1954).Google Scholar
  7. 7.
    H. K. MILLER and H. WAELSCH, J. Amer. Chem. Soc., 74, 1092 (1952).Google Scholar
  8. 8.
    J. D. CIPERA and R. V. V. NICHOLLS, Chem. and Ind., 16 (1955).Google Scholar
  9. 9.
    R. G. HISKEY and J. B. ADAMS, J. Amer. Chem. Soc., 87, 3969 (1965).Google Scholar
  10. 10.
    H. VON BRAMER and M. L. CLEMENS, U.S. Patent 2,615,042 (1952);Google Scholar
  11. 10a.
    H. VON BRAMER and M. L. CLEMENS, Chem. Abs., 47, 9362a (1953).Google Scholar
  12. 11.
    P.J. MILL and W. R. C. CRIMMIN, Biochim. Biophys. Acta, 23, 432 (1957).Google Scholar
  13. 12.
    H.J. BROWN and N. B. LORETTE, J. Org. Chem., 24, 261 (1959).Google Scholar
  14. 13.
    F. ZETZSCHE and A. FREDRICH, Chem. Ber., 72, 1735 (1949).Google Scholar
  15. 14.
    M. SMITH, J. G. MOFFATT, and H. G. KHORANA, J. Amer. Chem. Soc., 80, 6204 (1958).Google Scholar
  16. 15.
    R. CAMBLE, R. GARNER, and G. T. YOUNG, J. Chem. Soc. (C), 1911 (1969).Google Scholar
  17. 16.
    F. WEYGand and K. HUNGER, Chem. Ber., 95, 1 (1962).Google Scholar
  18. 17.
    R. B. WOODWARD, K. HEUSLER, J. GOSTELI, P. NAEGELI, W. OPPOLZER, R. RAMAGE, S. RANGANATHAN, and H. VORBRüGGEN, J. Amer. Chem. Soc., 88, 852 (1966).Google Scholar
  19. 18.
    R. B. WOODWARD, Science, 153, 487 (1966).Google Scholar
  20. 19.
    A. W. MILLER and C. J. M. STIRLING, J. Chem. Soc. (C), 2612 (1968).Google Scholar
  21. 20.
    E. VOWINKEL, Chem. Ber., 100, 16 (1967).Google Scholar
  22. 21.
    H. STAAB, Angew. Chem. Internat. Edn., 1, 351 (1962).Google Scholar
  23. 22.
    H. STAAB, Angew. Chem., 71, 194 (1959).Google Scholar
  24. 23.
    E. J. BOURNE, M. STACEY, J. C. TATLOW, and J. M. TEDDER, J. Chem. Soc., 2976 (1949).Google Scholar
  25. 24.
    J. M. TEDDER, Chem. Rev., 55, 787 (1955).Google Scholar
  26. 25.
    T. GRAMSTAD and R. N. HASZELDINE, J. Chem. Soc., 4069 (1957).Google Scholar
  27. 26.
    B. R. REIGEL, R. B. MOFFETT, and A. V. MCINTOSH, Org. Synth. Coll. Vol. 3, 237 (1955).Google Scholar
  28. 27.
    J. H. BREWSTER and C. J. CIOTTI, J. Amer. Chem. Soc., 77, 6214 (1955).Google Scholar
  29. 28.
    E. TASCHNER and G. WASIELEWSKI, Annalen, 640, 139 (1961).Google Scholar
  30. 29.
    R. P. PATEL and S. PRICE, J. Org. Chem., 30, 3575 (1965).Google Scholar
  31. 30.
    E. TASCHNER, J. F. BIERNAT, B. RZESZOTARSKA, and C. WASIELEWSKI, Annalen, 646, 123 (1961).Google Scholar
  32. 31.
    C. RAHA, Org. Synth. Coll. Vol. 4, 263 (1963).Google Scholar
  33. 32.
    D. S. BRESLOW, E. BAUMGARTEN, and C. R. HAUSER, J. Amer. Chem. Soc., 66,1286 (1944).Google Scholar
  34. 33.
    R. E. IRELand and M. CHAYKOVSKY, Org. Synth. 41, 5 (1962).Google Scholar
  35. 34.
    C. R. HAUSER, B. E. HUDSON, B. ABRAMOVITCH, and J. C. SHIVERS, Org. Synth. Coll. Vol. 3, 142 (1955).Google Scholar
  36. 35.
    M. BERGMANN, L. ZERVAS, and L. SALZMANN, Chem. Ber., 66, 1288(1933).Google Scholar
  37. 36.
    G. L. MILLER, O. K. BEHRENS, and V. DU VIGNEAUD, J. Biol. Chem., 140,411 (1941).Google Scholar
  38. 37.
    Y. IWAKURA, K. HAYASHI, S. KANG, and K. NAKAOJI, Bull. Chem. Soc. Japan, 37, 1707 (1964).Google Scholar
  39. 38.
    M. REGITZ, J. HOCKER, and A. LIEDHEGENER, Org. Synth. 48, 36(1968).Google Scholar
  40. 39.
    H. SCHULZ, Chem. Ber., 99, 3425 (1966).Google Scholar
  41. 40.
    G. C. STELAKATOS and N. ARGYROPOULOS, J. Chem. Soc. (C), 964 (1970).Google Scholar
  42. 41.
    E. WüNSCH and A. ZWICK, Chem. Ber., 97, 2497 (1964).Google Scholar
  43. 42.
    F. H. C. STEWART, Austral. J. Chem., 19, 1067, 1511, 2373 (1966);Google Scholar
  44. 42a.
    F. H. C. STEWART, Austral. J. Chem., 20, 365 (1967).Google Scholar
  45. 43a.
    F. H. C. STEWART, Austral. J. Chem., 21, 1327, 1639 (1968);Google Scholar
  46. 43b.
    F. H. C. STEWART, Austral. J. Chem., 22, 1291 (1969).Google Scholar
  47. 44.
    K. D. BERLIN, L. H. GOWER, J. W. WHITE, D. E. GIBBS, and G. P. STURM, J. Org. Chem., 27, 3595 (1962).Google Scholar
  48. 45.
    G. C. STELAKATOS, A. PAGANOU, and L. ZERVAS, J. Chem. Soc. (C), 1191,(1966).Google Scholar
  49. 46.
    P. BAMBERG, B. ECKSTRöM, and B. SJöBERG, Acta Chem. Scand., 21, 2210 (1967).Google Scholar
  50. 47.
    D. H. R. BARTON, Y. L. CHOW, A. COX, and G. W. KIRBY, J. Chem. Soc., 3571 (1965).Google Scholar
  51. 48.
    G. H. L. NEFKENS, G. I. TESSER, and R. J. F. NIVARD, Rec. Trav. Chim., 82, 941 (1963).Google Scholar
  52. 49.
    R. E. BOWMAN and W. D. FORDHAM, J. Chem. Soc., 2758 (1951).Google Scholar
  53. 50.
    E. TASCHNER, C. WASIELEWSKI, and J. F. BIERNAT, Annalen, 646,119(1961).Google Scholar
  54. 51.
    E. TASCHNER, A. CHIMIAK, B. BATOR, and T. SOKOLOWSKA, Annalen, 646, 134(1961).Google Scholar
  55. 52.
    D. E. AMES, G. HALL, and B. T. WARREN, J. Chem. Soc. (C), 2617 (1968).Google Scholar
  56. 53.
    A. L. MCCLOSKEY, G. S. FONKEN, R. W. KLUIBER, and W. S. JOHNSON, Org. Synth. Coll. Vol. 4, 261 (1963).Google Scholar
  57. 54.
    R. ROESKE, J. Org. Chem., 28, 1251 (1963).Google Scholar
  58. 55.
    R. SCHWYZER and H. RAPPELER, Helv. Chim. Acta, 44, 1991 (1961).Google Scholar
  59. 56.
    D. DAVIDSON and S. A. BERNHARD, J. Amer. Chem. Soc., 70, 3426(1943).Google Scholar
  60. 57.
    J. A. HEDGE, G. W. KRUSE, and H. R. SNYDER, J. Org. Chem., 26,992,3166(1961).Google Scholar
  61. 58.
    C. G. OVERBERGER and J.-P. ANSELME, J. Org. Chem., 28, 592 (1963).Google Scholar
  62. 59.
    E. HARDEGGER, Z. EL. HEWEIHI, and F. G. ROBINET, Helv. Chim. Acta, 31, 439 (1948).Google Scholar
  63. 60.
    J. B. MILLER, J. Org. Chem., 24, 560 (1959).Google Scholar
  64. 61.
    C. D. GUTSCHE, Org. Reactions, 8, 364 (1954).Google Scholar
  65. 62.
    D. T. WITIAK and B. K. SINHA, J. Org. Chem., 35, 501 (1970).Google Scholar
  66. 63.
    R. GREWE and A. BOKRANZ, Chem. Ber., 88, 49 (1955).Google Scholar
  67. 64.
    J. F. W. KEANA and C. U. KIM, J. Org. Chem., 35, 1093 (1970).Google Scholar
  68. 65.
    E. VOWINKEL, Chem. Ber., 95, 2997 (1962).Google Scholar
  69. 66.
    H. BRECHBüHLER, H. BüCHI, E. HATZ, J. SCHREIBER, and A. ESCHENMOSER, Helv. Chim. Acta, 48, 1746 (1965).Google Scholar
  70. 67.
    A. MICHAEL and N. WEINER, J. Amer. Chem. Soc., 58, 680 (1936).Google Scholar
  71. 68.
    R. U. LEMIEUX, Canad. J. Chem., 31, 396 (1953).Google Scholar
  72. 69.
    L. F. AUDRIETH and M. V. SVEDA, Org. Synth. Coll. Vol. 3, 536 (1955).Google Scholar
  73. 70.
    R. GREWE, W. LORENZEN, and L. VINING, Chem. Ber., 87, 793 (1954).Google Scholar
  74. 71.
    H. EGGERER and C. GRüNEWäLDER, Annalen, 677, 200 (1964).Google Scholar
  75. 72.
    D. E. AMES and P. J. ISLIP, J. Chem. Soc., 351, 4409 (1961);Google Scholar
  76. 72a.
    D. E. AMES and P. J. ISLIP, J. Chem. Soc., 351, 4363 (1963).Google Scholar
  77. 73.
    J. M. OSBOND, P. G. PHILPOTT, and J. S. WICKENS, J. Chem. Soc., 2779 (1961).Google Scholar
  78. 74.
    R. E. STRANGE and L. H. KENT, Biochem. J., 71, 333 (1959).Google Scholar
  79. 75.
    H. STETTER and K. H. STEINACKER, Chem. Ber., 86, 790 (1953);Google Scholar
  80. 75a.
    H. STETTER and K. H. STEINACKER, Chem. Ber., 87, 205 (1954).Google Scholar
  81. 76.
    H. STETTER and K. H. STEINACKER, Chem. Ber., 87, 205 (1954).Google Scholar
  82. 77.
    H. MEERWEIN, R. BORNER, O. FUCHS, H. JüRGEN, SASSE, H. SCHRODT, and J. SPILLE, Chem. Ber., 89, 2060 (1956).Google Scholar
  83. 78.
    K. BODENBENNER, Annalen, 623, 183 (1959).Google Scholar
  84. 79.
    R. A. LE MAHIEU and R. W. KIERSTEAD, Tetrahedron Letters, 5111 (1970).Google Scholar
  85. 80.
    A. C. COPE, H. L. HOLMES, and H. O. HOUSE, Org. Reactions 9, 107(1957).Google Scholar
  86. 81.
    C. R. HAUSER, F. W. SWAMER, and J. T. ADAMS, Org. Reactions, 8,59 (1954).Google Scholar
  87. 82.
    A. MAERCKER, Org. Reactions, 14, 270 (1965).Google Scholar
  88. 83.
    J. P. SCHAEFFER and J. J. BLOOMFIELD, Org. Reactions, 17, 1 (1965).Google Scholar
  89. 84.
    B. RIEGEL and W. M. LILIENFIELD, J. Amer. Chem. Soc., 67, 1273(1945).Google Scholar
  90. 85.
    W. J. BAILEY and J. J. DALY, J. Org. Chem., 22, 1189 (1957);Google Scholar
  91. 85a.
    W. J. BAILEY and J. J. DALY, J. Org. Chem., 29, 1249(1964).Google Scholar
  92. 86.
    R. F. NEILSEN, J. Amer. Chem. Soc., 58, 206 (1936).Google Scholar
  93. 87.
    B. C. L. WEEDON, Quart. Rev., 6, 380 (1952).Google Scholar
  94. 88.
    A. J. PARKER, Chem. Rev., 69, 1 (1969).Google Scholar
  95. 89.
    D. D. ROBERTS, J. Org. Chem., 29, 2039, 2714 (1964);Google Scholar
  96. 89a.
    D. D. ROBERTS, J. Org. Chem., 30, 3516 (1965);Google Scholar
  97. 89b.
    D. D. ROBERTS, J. Org. Chem., 31, 4037 (1966).Google Scholar
  98. 90.
    F. C. CHANG and N. F. WOOD, Tetrahedron Letters, 2969 (1964).Google Scholar
  99. 91.
    F. ELSINGER, J. SCHREIBER, and A. ESCHENMOSER, Helv. Chim. Acta, 43, 113 (1960).Google Scholar
  100. 92.
    P. D. G. DEAN, J. Chem. Soc., 6655 (1965).Google Scholar
  101. 93.
    P. A. BARTLETT and W. S. JOHNSON, Tetrahedron Letters, 4459 (1970).Google Scholar
  102. 94.
    L. RUZICKA and H. GUBSER, Helv. Chim. Acta, 27, 1054 (1945).Google Scholar
  103. 95.
    L. PANIZZI, M. L. SCARPATI, and G. ORIENTE, Experientia, 11, 383 (1955).Google Scholar
  104. 96.
    L. BOHLMANN and W. SUCROW, Chem. Ber., 97, 1839, 1846 (1964).Google Scholar
  105. 97.
    H. G. WALKER and C. R. HAUSER, J. Amer. Chem. Soc., 68, 1386 (1946).Google Scholar
  106. 98.
    A. MICHAEL, J. Amer. Chem. Soc., 14, 510 (1892).Google Scholar
  107. 99.
    G. M. ROBINSON and R. ROBINSON, J. Chem. Soc., 175 (1925).Google Scholar
  108. 100.
    H. O. HOUSE Modern Synthetic Reactions (Benjamin, New York, Amsterdam, 1965), p. 170.Google Scholar
  109. 101.
    M. J. S. A. AMARAL, G. C. BARRETT, H. N. RYDON, and J. E. WILLETT, J. Chem. Soc. (C), 807 (1966).Google Scholar
  110. 102.
    M.J. S. A. AMARAL, J. Chem. Soc. (C), 2495 (1969).Google Scholar
  111. 103.
    P. M. HARDY, H. N. RYDON, and R. C. THOMPSON, Tetrahedron Letters, 2525 (1968).Google Scholar
  112. 104.
    G. S. FONKEN and W. S. JOHNSON, J. Amer. Chem. Soc., 74, 831 (1952).Google Scholar
  113. 105.
    E. R. CLARK and J. G. B. HOWES, J. Chem. Soc., 1152 (1956).Google Scholar
  114. 106.
    S. O. LAWESSON, E. H. LARSEN, G. SUNDSTRöM, and H. J. JACKOBSEN, Acta Chem. Scand, 17, 2216 (1963).Google Scholar
  115. 107.
    S. O. LAWESSON and S. GRöNWALL, Acta Chem. Scand., 14, 1445 (1960).Google Scholar
  116. 108.
    S. O. LAWESSON, S. GRöNWALL, and R. SandBERG, Org. Synth., 42, 28 (1963).Google Scholar
  117. 109.
    H. WIELand and H. DETERMAN, Angew. Chem. Internat. Edn., 2, 58 (1963).Google Scholar
  118. 110.
    R. SCHWYZER and H. DIETRICH, Helv. Chim. Acta, 44, 2003 (1961).Google Scholar
  119. 111.
    P. M. BRYANT, R. H. MOORE, P.J. PIMLOTT, and G. T. YOUNG, J. Chem. Soc., 3868 (1959).Google Scholar
  120. 112.
    R. E. BOWMAN, J. Chem. Soc., 177, 325 (1950).Google Scholar
  121. 113.
    D. E. AMES and R. E. BOWMAN, J. Chem. Soc., 1079, 1087 (1951).Google Scholar
  122. 114.
    J. E. SHIELDS, W. H. MCGREGOR, and F. H. CARPENTER, J. Org. Chem., 26, 1491 (1961).Google Scholar
  123. 115.
    F. H. C. STEWART, Austral. J. Chem., 18, 1699 (1965).Google Scholar
  124. 116.
    E. HASLAM, R. D. HAWORTH, and G. K. MAKINSON, J. Chem. Soc., 5153 (1961).Google Scholar
  125. 117.
    E. HASLAM, R. D. HAWORTH, and D. A. LAWTON, J. Chem. Soc., 2173(1963).Google Scholar
  126. 118.
    P. W. CRABTREE, E. HASLAM, R. D. HAWORTH, S. D. MILLS, and J. E. STANGROOM, J. Chem. Soc., 6888 (1965).Google Scholar
  127. 119.
    J. B. HENDRICKSON and C. KandALL, Tetrahedron Letters, 343 (1970).Google Scholar
  128. 120.
    D. L. TURNER and E. BACZYNSKI, Chem. and Ind., 1204, (1970).Google Scholar
  129. 121.
    R. SCHWYZER, B. ISELIN, and M. FEURER, Helv. Chim. Acta, 38, 69 (1955).Google Scholar
  130. 122.
    J. C. SHEEHAN and G. D. DAVES, J. Org. Chem., 29, 2006 (1964).Google Scholar
  131. 123.
    G. LOSSE and S. BERNDSEN, Annalen, 715, 204 (1968).Google Scholar
  132. 124.
    J. A. BARLTROP, P. J. PLANT, and P. SCHOFIELD, Chem. Comm., 822 (1966).Google Scholar
  133. 125.
    D. H. R. BARTON, T. NAKANO, and P. G. SAMMES, J. Chem. Soc. (C), 322 (1968).Google Scholar
  134. 126.
    H. R. SNYDER and C. W. KRUSE, J. Amer. Chem. Soc., 80, 1942 (1958).Google Scholar
  135. 127.
    H. KATSURA, Nippon Kagaku Zasshi, 77, 1105 (1956) (Chem. Abs. 53,5126(1959)).Google Scholar
  136. 128.
    H. O. L. FISCHER and G. DANGSCHAT, Chem. Ber., 65, 1009 (1932).Google Scholar
  137. 129.
    H. O. L. FISCHER and G. DANGSCHAT, Helv. Chim. Acta., 17, 1197 (1934).Google Scholar
  138. 130.
    R. H. BAKER and F. G. BORDWELL, Org. Synth. Coll. Vol. 3, 141 (1955).Google Scholar
  139. 131.
    R. LEDGER and F. H. C. STEWART, Austral. J. Chem., 18, 1477 (1965).Google Scholar
  140. 132.
    F. H. C. STEWART, Austral. J. Chem., 21, 2543 (1968).Google Scholar
  141. 133.
    W. E. CONRAD and S. M. DEC, J. Org. Chem., 23, 1700 (1958).Google Scholar
  142. 134.
    G. S. HAMMOND and G. T. RUDESILL, J. Amer. Chem. Soc., 72, 2769 (1950).Google Scholar
  143. 135.
    C. W. ROBERTS, J. Amer. Chem. Soc., 76, 6203 (1954).Google Scholar
  144. 136.
    J. H. JONES and G. T. YOUNG, J. Chem. Soc. (C), 436 (1968).Google Scholar
  145. 137.
    P. J. CROOK, A. H. JACKSON, and G. W. KENNER, J. Chem. Soc. (C), 474 (1971).Google Scholar
  146. 138.
    R. P. CARR, A. H. JACKSON, G. W. KENNER, and G. S. SACH, J. Chem. Soc. (C), 487 (1971).Google Scholar
  147. 139.
    E. TASCHNER and B. RZESZOTARSKA, Angew. Chem. Internat. Edn., 4, 594 (1965).Google Scholar
  148. 140.
    G. W. ANDERSON, J. E. ZIMMERMAN, and F. C. CALLAHAN, J. Amer. Chem. Soc., 86, 1839 (1964).Google Scholar
  149. 141.
    G. H. L. NEFKENS, G. I. TESSER, and R. J. F. NIVARD, Rec. Trav. Chim., 81, 683 (1962).Google Scholar
  150. 142.
    B. O. HandFORD, J. H. JONES, G. T. YOUNG, and T. F. N. JOHNSON, J. Chem. Soc., 6814 (1965).Google Scholar
  151. 143.
    G. R. FOSKER, K. D. HARDY, J. H. C. NAYLER, P. SEGGERY, and E. R. STOVE, J. Chem. Soc. (C), 1917 (1971).Google Scholar
  152. 144.
    B. FECHTIG, H. PETER, H. BICKEL, and E. VISCHER, Helv. Chim.Acta, 51, 1108 (1968).Google Scholar
  153. 145.
    H. W. O. WEISSENBURGER and M. G. VAN DER HOEVEN, Rec. Trav. Chim., 89, 1081 (1970).Google Scholar
  154. 146.
    A. I. MEYERS, I. R. POLITZER, B. K. BandLISH, and G. R. MALONE, J. Amer. Chem. Soc., 91, 5886 (1969).Google Scholar
  155. 147.
    A. I. MEYERS and D. L. TEMPLE, J. Amer. Chem. Soc., 92, 6644, 6646(1970).Google Scholar
  156. 148.
    M. FRANKEL, D. GERTNER, D. WAGNER, and A. ZILKHA, J. Org. Chem., 30, 1596 (1965).Google Scholar
  157. 149.
    P. BAMBERG, B. EKSTRÖM, and B. SJÖBERG, Acta Chem. Scand., 22, 367 (1968).Google Scholar

Copyright information

© Plenum Publishing Company Ltd 1973

Authors and Affiliations

  • E. Haslam
    • 1
  1. 1.Department of ChemistryUniversity of SheffieldSheffieldEngland

Personalised recommendations