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Asymmetric Autocatalysis with Amplification of Chirality

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Amplification of Chirality

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 284))

Abstract

We found that chiral 5-pyrimidyl alkanols are highly enantioselective asymmetric autocatalysts forthe addition of i-Pr2Zn to the corresponding aldehyde.Asymmetric autocatalysis with amplification of ee from extremely low (0.00005%) ee to >99.5% ee wasrealized for the first time by consecutive asymmetric autocatalysis. The chirality of CPL was directlycorrelated with the chirality of the pyrimidyl alkanol with high ee by asymmetric photodegradation of theracemic pyrimidyl alkanol in combination with asymmetric autocatalysis. Chiral inorganic crystals suchas quartz act as chiral triggers and regulate the sense of the asymmetric autocatalysis. Chiral organiccrystals composed of an achiral compound such as hippuric acid act as the initial source of chirality forasymmetric autocatalysis to produce the nearly enantiomerically pure product. Highly sensitive chiral discriminationof amino acids with low ee is described. Direct examination of extraterrestrial chirality was performedon meteorites by applying asymmetric autocatalysis as the chiral sensor. Spontaneous absolute asymmetricsynthesis is described in the formation of enantiomerically enriched pyrimidyl alkanol from the reactionof pyrimidine-5-carbaldehyde and i-Pr2Zn withoutadding any chiral substance in combination with asymmetric autocatalysis. Asymmetric autocatalysis of a chiralpyrimidyl alkanol is the only possible method to discriminate a cryptochiral quaternary saturated hydrocarbon,whose chirality is not capable of determination by any current method. The discrimination of chiralitydue to deuterium substitution is also accessible by the highly sensitive asymmetric autocatalysis.

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References

  1. Maddox J (1998) What Remains to Be Discovered: Mapping the Secrets of the Universe, the Origins of Life, and the Future of the Human Race, Free Press

    Google Scholar 

  2. Kuhn W, Knopf EZ (1930) Phys Chem B 7:292

    CAS  Google Scholar 

  3. Bernstein WJ, Calvin M, Buchardt O (1972) J Am Chem Soc 94:494

    CAS  Google Scholar 

  4. Inoue Y (1992) Chem Rev 92:741

    CAS  Google Scholar 

  5. Bonner WA, Rubenstein E (1987) BioSystems 20:99

    CAS  Google Scholar 

  6. Feringa BL, van Delden RA (1999) Angew Chem Int Ed 38:3418

    Google Scholar 

  7. Hazen RM (2004) Chiral Crystal Faces of Common Rock-Forming Minerals In: Palyi G, Zucchi C (eds) Progress in Biological Chirality, chap 9. Elsevier, Oxford, pp 137–151

    Google Scholar 

  8. Cairns-Smith AG (1986) Chem Ber, p 559

    Google Scholar 

  9. Green BS, Lahav M, Rabinovich D (1972) Acc Chem Res 12:191

    Google Scholar 

  10. Matsuura T, Koshima H (2005) J Photochem Photobiol C: Photochem Rev 6:7

    CAS  Google Scholar 

  11. Tanaka K, Toda F (2000) Chem Rev 100:1025

    CAS  Google Scholar 

  12. Sakamoto M (1997) Chem Eur J 3:684

    CAS  Google Scholar 

  13. Hasegawa M (1983) Chem Rev 83:507

    CAS  Google Scholar 

  14. Mislow K (2003) Collect Czech Chem Commun 68:849–864

    CAS  Google Scholar 

  15. Islas JS, Lavabre D, Grevy JM, Lamoneda RH, Cabrera HR, Micheau JC, Buhse T (2005) Proc Natl Acad Sci 102:13743

    CAS  Google Scholar 

  16. Mason SF, Tranter GE (1984) Mol Phys 53:1091

    CAS  Google Scholar 

  17. Frank FC (1953) Biochim Biophys Acta 11:459

    CAS  Google Scholar 

  18. Soai K, Shibata T (1999) Asymmetric autocatalysis and biomolecular chirality. In: Pályi G, Zucchi C, Caglioti L (eds) Advances in biochirality, chap 11. Elsevier, Oxford, p 125

    Google Scholar 

  19. Soai K, Shibata T, Sato I (2000) Acc Chem Res 33:382

    CAS  Google Scholar 

  20. Soai K (1999) Enantiomer 4:591

    CAS  Google Scholar 

  21. Soai K, Shibata T (1997) J Synth Org Chem Jpn 55:994

    CAS  Google Scholar 

  22. Soai K Shibata T (2000) Asymmetric amplification and autocatalysis In: Ojima I (ed) Catalytic asymmetric synthesis, 2nd ed, chap 9. Wiley-VCH, New York, p 699

    Google Scholar 

  23. Soai K, Shibata T, Sato I (2001) J Chem Soc Jpn, Chem Ind Chem, p 141

    Google Scholar 

  24. Soai K, Sato I, Shibata T (2001) Chem Record 1:321

    CAS  Google Scholar 

  25. Soai K, Sato I (2002) Chirality 14:548

    CAS  Google Scholar 

  26. Soai K (2002) Asymmetric autocatalysis and the origin of chiral homogeneity of biologically relevant molecules. In: Pályi G, Zucchi C, Caglioti L (eds) Fundamentals of life. Elsevier, Paris, p 427

    Google Scholar 

  27. Soai K, Sato I, Shibata T (2002) J Synth Org Chem Jpn 60:668

    CAS  Google Scholar 

  28. Soai K, Sato I (2002) Viva Origino 30:186

    CAS  Google Scholar 

  29. Soai K, Sato I, Shibata T (2004) Asymmetric autocatalysis and the origin of homochirality of biomolecules. In: Malhotra SV (ed) Methodologies in asymmetric catalysis. J Am Chem Soc, Washington, DC, p 85

    Google Scholar 

  30. Soai K (2004) J Synth Org Chem Jpn 62:673

    CAS  Google Scholar 

  31. Soai K, Shibata T, Sato I (2004) Bull Chem Soc Jpn 77:1063

    CAS  Google Scholar 

  32. Soai K, Kawasaki T (2006) Chirality 18:469

    CAS  Google Scholar 

  33. Soai K, Kawasaki T (2006) Shokubai (Catalysts & Catalysis) 48:346

    CAS  Google Scholar 

  34. Bolm C, Bienewald F, Seger A (1996) Angew Chem Int Ed Engl 35:1657

    CAS  Google Scholar 

  35. Avalos M, Babiano R, Cintas P, Jiménez JL, Palacios JC (2000) Chem Commun, p 887

    Google Scholar 

  36. Buschmann H, Thede R, Heller D (2000) Angew Chem Int Ed 39:4033

    CAS  Google Scholar 

  37. Todd MH (2002) Chem Soc Rev 31:211

    CAS  Google Scholar 

  38. Blackmond DG (2004) Proc Nat Acad Sci 101:5732

    CAS  Google Scholar 

  39. Podlech J, Gehring T (2005) Angew Chem Int Ed 44:5776

    CAS  Google Scholar 

  40. Mikami K, Yamanaka M (2003) Chem Rev 103:3369

    CAS  Google Scholar 

  41. Gridnev ID (2006) Chem Lett 35:148

    CAS  Google Scholar 

  42. Caglioti L, Zucchi C, Pályi G (2005) Chemistry Today (Chimica Oggi) 23:38

    CAS  Google Scholar 

  43. Pályi G, Micskei K, Zékány L, Zucchi C, Caglioti L (2005) Magy Kem Lapja 60:17

    Google Scholar 

  44. Stankiewicz J, Eckardt LH (2006) Angew Chem Int Ed 45:342

    CAS  Google Scholar 

  45. Jacobsen EN, Pfaltz A, Yamamoto H (1999) Comprehensive asymmetric catalysis. Springer-Verlag, Heidelberg

    Google Scholar 

  46. Ojima I (2000) Catalytic asymmetric synthesis, 2nd edn. Wiley, New York

    Google Scholar 

  47. Malhotra SV (2004) Methodologies in asymmetric catalysis. J Am Chem Soc, Washington, DC

    Google Scholar 

  48. Soai K, Niwa S (1992) Chem Rev 92:833

    CAS  Google Scholar 

  49. Noyori R, Kitamura M (1991) Angew Chem Int Ed 30:49

    Google Scholar 

  50. Pu L, Yu HB (2001) Chem Rev 101:757

    CAS  Google Scholar 

  51. Mukaiyama T, Soai K, Sato T, Shimizu H, Suzuki K (1979) J Am Chem Soc 101:1455

    CAS  Google Scholar 

  52. Soai K, Yokoyama S, Ebihara K, Hayasaka T, (1987) J Chem Soc Chem Commun, p 1690

    Google Scholar 

  53. Soai K, Yokoyama S, Hayasaka T (1991) J Org Chem 56:4264

    CAS  Google Scholar 

  54. Soai K, Hayase T, Takai K, Sugiyama T (1994) J Org Chem 59:7908

    CAS  Google Scholar 

  55. Soai K, Ookawa A, Ogawa K, Kaba T (1987) J Chem Soc, Chem Commun, p 467

    Google Scholar 

  56. Soai K, Ookawa A, Kaba T, Ogawa K (1987) J Am Chem Soc 109:7111

    CAS  Google Scholar 

  57. Soai K, Hori S, Niwa S (1989) Heterocycles 29:2065

    CAS  Google Scholar 

  58. Shibata T, Choji K, Morioka H, Hayase T, Soai K (1996) Chem Commun, p 751

    Google Scholar 

  59. Shibata T, Morioka H, Tanji S, Hayase T, Kodaka Y, Soai K (1996) Tetrahedron Lett 37:8783

    CAS  Google Scholar 

  60. Shibata T, Morioka H, Hayase T, Choji K, Soai K (1996) J Am Chem Soc 118:471

    CAS  Google Scholar 

  61. Soai K, Shibata T, Morioka H, Choji K (1995) Nature 378:767

    CAS  Google Scholar 

  62. Shibata T, Hayase T, Yamamoto J, Soai K (1997) Tetrahedron: Asymm 8:1717

    CAS  Google Scholar 

  63. Shibata T, Yonekubo S, Soai K (1999) Angew Chem Int Ed 38:659

    CAS  Google Scholar 

  64. Sato I, Urabe H, Ishiguro S, Shibata T, Soai K (2003) Angew Chem Int Ed 42:315

    CAS  Google Scholar 

  65. Lutz F, Kawasaki T, Soai K (2006) Tetrahedron: Asymm 17:486

    CAS  Google Scholar 

  66. Sato I, Yanagi T, Soai K (2002) Chirality 14:166

    CAS  Google Scholar 

  67. Sato I, Omiya D, Tsukiyama K, Ogi Y, Soai K (2001) Tetrahedron: Asymm 12:1965

    CAS  Google Scholar 

  68. Sato I, Omiya D, Igarashi H, Kato K, Ogi Y, Tsukiyama K, Soai K (2003) Tetrahedron: Asymm 14:975

    CAS  Google Scholar 

  69. Gridnev ID, Serafimov JM, Brown JM (2004) Angew Chem Int Ed 43:4884

    CAS  Google Scholar 

  70. Blackmond DG (2004) Proc Natl Acad Sci 101:5732

    CAS  Google Scholar 

  71. Buhse T (2003) Tetrahedron: Asymm 14:1055

    CAS  Google Scholar 

  72. Saito Y, Hyuga H (2004) J Phys Soc Jpn 73:33

    CAS  Google Scholar 

  73. Lente G (2005) J Phys Chem A 109:11058

    CAS  Google Scholar 

  74. Micskei K, Pota G, Caglioti L, Palyi G (2006) J Phys Chem A 110:5982

    CAS  Google Scholar 

  75. Shibata T, Yamamoto J, Matsumoto N, Yonekubo S, Osanai S, Soai K (1998) J Am Chem Soc 120:12157

    CAS  Google Scholar 

  76. Kawasaki T, Shimizu M, Suzuki K, Sato I, Soai K (2004) Tetrahedron: Asymm 15:3699

    CAS  Google Scholar 

  77. Kawasaki T, Suzuki K, Licandro E, Bossi A, Maiorana S, Soai K (2006) Tetrahedron Asymm 17:2050

    CAS  Google Scholar 

  78. Bailey J, Chrysostomou A, Hough JH, Gledhill TM, McCall A, Clark S, Menard F, Tamura M (1998) Science 281:672

    CAS  Google Scholar 

  79. Nishino H, Kosaka A, Hembury GA, Aoki F, Miyauchi K, Shitomi H, Onuki H, Inoue Y (2002) J Am Chem Soc 124:11618

    CAS  Google Scholar 

  80. Suarez M, Schuster GB (1995) J Am Chem Soc 117:6732

    CAS  Google Scholar 

  81. Kagan H, Moradpour A, Nicoud JF, Balavoine G, Tsoucaris G (1971) J Am Chem Soc 93:2353

    CAS  Google Scholar 

  82. Soai K, Sato I (2001) Enantiomer 6:189

    CAS  Google Scholar 

  83. Sato I, Ohgo Y, Igarashi H, Nishiyama D, Kawasaki T, Soai K (2007) J Organomet Chem 692:1783

    CAS  Google Scholar 

  84. Sato I, Yamashima R, Kadowaki K, Yamamoto J, Shibata T, Soai K (2001) Angew Chem Int Ed 40:1096

    CAS  Google Scholar 

  85. Sato I, Sugie R, Matsueda Y, Furumura Y, Soai K (2004) Angew Chem Int Ed 43:4490

    CAS  Google Scholar 

  86. Kawasaki T, Sato M, Ishiguro S, Saito T, Morishita Y, Sato I, Nishino H, Inoue Y, Soai K (2005) J Am Chem Soc 127:3274

    CAS  Google Scholar 

  87. Hazen RM (2004) Chiral crystal faces of common rock-forming minerals In: Palyi G, Zucchi C (eds) Progress in biological chirality, chap 9. Elsevier, Oxford, p 137

    Google Scholar 

  88. Bonner WA, Kavasmaneck PR, Martin FS, Flores JJ (1974) Science 186:143

    CAS  Google Scholar 

  89. Soai K, Osanai S, Kadowaki K, Yonekubo S, Shibata T, Sato I (1999) J Am Chem Soc 121:11235

    CAS  Google Scholar 

  90. Pagni RM, Compton RN (2002) Cryst Growth Des 2:249

    CAS  Google Scholar 

  91. Kondepudi DK, Kaufman RJ, Singh N (1990) Science 250:975

    CAS  Google Scholar 

  92. Sato I, Kadowaki K, Soai K (2000) Angew Chem Int Ed 39:1510

    CAS  Google Scholar 

  93. Sato I, Kadowaki K, Ohgo Y, Soai K (2004) J Mol Cat A Chem 216:209

    CAS  Google Scholar 

  94. Penzien K, Schmidt GM (1969) Angew Chem Int Ed 8:608

    CAS  Google Scholar 

  95. Ringertz H (1971) Acta Crystallogr Sec B 27:285

    CAS  Google Scholar 

  96. Kawasaki T, Suzuki K, Hatase K, Otsuka M, Koshima H, Soai K (2006) Chem Commun, p 1869

    Google Scholar 

  97. Koshima H, Hayashi E, Matsuura T, Tanaka K, Toda F, Kato M, Kiguchi M (1997) Tetrahedron Lett 38:5009

    CAS  Google Scholar 

  98. Koshima H, Nagano M, Asahi T (2005) J Am Chem Soc 127:2455

    CAS  Google Scholar 

  99. Kawasaki T, Jo K, Igarashi H, Sato I, Nagano M, Koshima H, Soai K (2005) Angew Chem Int Ed 44:2774

    CAS  Google Scholar 

  100. Cronin JR, Pizzarello S (1997) Science 275:951

    CAS  Google Scholar 

  101. Kawasaki T, Hatase K, Fujii Y, Jo K, Soai K, Pizzarello S (2006) Geochim Cosmochim Acta 70:5395

    CAS  Google Scholar 

  102. Mills WH (1932) Chem Ind 51:750

    CAS  Google Scholar 

  103. Soai K, Shibata T, Kowata Y (1997) JP Patent 9268179

    Google Scholar 

  104. Soai K, Sato I, Shibata T, Komiya S, Hayashi M, Matsueda Y, Imamura H, Hayase T, Morioka H, Tabira H, Yamamoto J, Kowata Y (2003) Tetrahedron: Asymm 14:185

    CAS  Google Scholar 

  105. Kawasaki T, Suzuki K, Shimizu M, Ishikawa K, Soai K (2006) Chirality 18:479

    CAS  Google Scholar 

  106. Eliel EL, Wilen SW (1994) Stereochemistry of Organic Compounds. Wiley, New York (Chap 4)

    Google Scholar 

  107. Wynberg H, Hekkert GL, Houbiers JPM, Bosch HW (1965) J Am Chem Soc 87:2635

    CAS  Google Scholar 

  108. Mislow K, Bickart P (1976–1977) Isr J Chem 15:1

    Google Scholar 

  109. Kawasaki T, Tanaka H, Tsutsumi T, Kasahara T, Sato I, Soai K (2006) J Am Chem Soc 128:6032

    CAS  Google Scholar 

  110. Nishio M, Hirota M, Umezawa Y (1998) The CH/p Interaction, Evidence, Nature, and Consequences. Wiley-VCH, New York

    Google Scholar 

  111. Sato I, Osanai S, Kadowaki K, Sugiyama T, Shibata T, Soai K (2002) Chem Lett 168

    Google Scholar 

  112. Sato I, Matsueda Y, Kadowaki K, Yonekubo S, Shibata T, Soai K (2002) Helv Chim Acta 85:3383

    CAS  Google Scholar 

  113. Sato I, Ahno A, Aoyama Y, Kasahara T, Soai K (2003) Org Biomol Chem 1:244

    CAS  Google Scholar 

  114. Tanji S, Ohno A, Sato I, Soai K (2001) Org Lett 3:287

    CAS  Google Scholar 

  115. Arigoni D, Eliel EL (1969) Top Stereochem 4:127

    CAS  Google Scholar 

  116. Verbit L (1970) Prog Phys Org Chem 7:51

    CAS  Google Scholar 

  117. Bartell LS, Roth EA, Hollowell CD, Kuchitsu K, Young JE Jr (1965) J Chem Phys 42:2683

    CAS  Google Scholar 

  118. Bartell L, Roskos RR (1966) J Chem Phys 44:457

    CAS  Google Scholar 

  119. Sato I, Omiya D, Saito T, Soai K (2000) J Am Chem Soc 122:11739

    CAS  Google Scholar 

  120. Davis ME (1993) Acc Chem Res 26:111

    CAS  Google Scholar 

  121. Davis ME, Katz A, Ahmad WR (1996) Chem Mater 8:1820

    CAS  Google Scholar 

  122. Thomas JM, Raja R (2001) Chem Commun, p 675

    Google Scholar 

  123. Wulff G (2002) Chem Rev 102:1

    CAS  Google Scholar 

  124. Sato I, Kadowaki K, Urabe H, Hwa Jung J, Ono Y, Shinkai S, Soai K (2003) Tetrahedron Lett 44:721

    CAS  Google Scholar 

  125. Soai K, Watanabe M, Yamamoto A (1990) J Org Chem 55:4832

    CAS  Google Scholar 

  126. Kawasaki T, Ishikawa K, Sekibata H, Sato I, Soai K (2004) Tetrahedron Lett 45:7939

    CAS  Google Scholar 

  127. Sato I, Shimizu M, Kawasaki T, Soai K (2004) Bull Chem Soc Jpn 77:1587

    CAS  Google Scholar 

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  1. Department of Applied Chemistry, Tokyo University of Science, Kagurazaka, Shinjuku-ku, 162-8601, Tokyo, Japan

    Kenso Soai & Tsuneomi Kawasaki

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  1. Kenso Soai
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  2. Tsuneomi Kawasaki
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Soai, K., Kawasaki, T. (2007). Asymmetric Autocatalysis with Amplification of Chirality . In: Soai, K. (eds) Amplification of Chirality. Topics in Current Chemistry, vol 284. Springer, Berlin, Heidelberg. https://doi.org/10.1007/128_2007_138

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