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Shvo’s Catalyst in Hydrogen Transfer Reactions

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Book cover Bifunctional Molecular Catalysis

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 37))

Abstract

This chapter reviews the use of ShvoB1;apos;s catalyst in various hydrogen transfer reactions and also discusses the mechanism of the hydrogen transfer. The Shvo catalyst is very mild to use since no activation by base is required in the transfer hydrogenation of ketones or imines or in the transfer dehydrogenation of alcohols and amines. The Shvo catalyst has also been used as an efficient racemization catalyst for alcohols and amines. Many applications of the racemization reaction are found in the combination with enzymatic resolution leading to a dynamic kinetic resolution (DKR). In these dynamic resolutions, the yield based on the starting material can theoretically reach 100%. The mechanism of the hydrogen transfer from the Shvo catalyst to ketones (aldehydes) and imines as well as the dehydrogenation of alcohols and amines has been studied in detail over the past decade. It has been found that for ketones (aldehydes) and alcohols, there is a concerted transfer of the two hydrogens involved, whereas for typical amines and imines, there is a stepwise transfer of the two hydrogens. One important question is whether the substrate is coordinated to the metal or not in the hydrogen transfer step(s). The pathway involving coordination to activate the substrate is called the inner-sphere mechanism, whereas transfer of hydrogen without coordination is called the outer-sphere mechanism. These mechanistic proposals together with experimental and theoretical studies are discussed.

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References

  1. Blum Y, Shvo Y (1984) Isr J Chem 24:144

    CAS  Google Scholar 

  2. Shvo Y, Czarkie D, Rahamim Y, Chodosh DF (1986) J Am Chem Soc 108:7400

    Article  CAS  Google Scholar 

  3. Menashe N, Shvo Y (1991) Organometallics 10:3885

    Article  CAS  Google Scholar 

  4. Samec JSM, Bäckvall J-E (2002) Chem Eur J 8:2955

    Article  CAS  Google Scholar 

  5. Samec JSM, Mony L, Bäckvall J-E (2005) Can J Chem 83:909

    Article  CAS  Google Scholar 

  6. Blum Y, Czarkie D, Rahamim Y, Shvo Y (1985) Organometallics 4:1459

    Article  CAS  Google Scholar 

  7. Wang G-Z, Andreasson U, Bäckvall J-E (1994) J Chem Soc Chem Commun:1037

    Google Scholar 

  8. Almeida MLS, Beller M, Wang G-Z, Bäckvall J-E (1996) Chem Eur J 2:1533

    Article  CAS  Google Scholar 

  9. Csjernyik G, éll AH, Fadini L, Pugin B, Bäckvall J-E (2002) J Org Chem 67:1657

    Article  CAS  Google Scholar 

  10. éll AH, Samec JSM, Brasse C, Bäckvall J-E (2002) Chem Commun:1144

    Google Scholar 

  11. éll AH, Johnson JB, Bäckvall J-E (2003) Chem Commun:1652B1;ndash;1653

    Google Scholar 

  12. Samec JSM, éll AH, Bäckvall J-E (2005) Chem Eur J 11:2327

    Article  CAS  Google Scholar 

  13. Larsson ALE, Persson BA, Bäckvall J-E (1997) Angew Chem Int Ed Engl 36:1211

    Article  CAS  Google Scholar 

  14. Persson BA, Larsson ALE, Ray ML, Bäckvall J-E (1999) J Am Chem Soc 121:1645

    Article  CAS  Google Scholar 

  15. Huerta FF, Minidis A, Bäckvall J-E (2001) Chem Soc Rev 30:321

    Article  CAS  Google Scholar 

  16. Pámies O, Bäckvall J-E (2003) Chem Rev 103:3247

    Article  Google Scholar 

  17. Kim MJ, Ahn Y, Park J (2002) Curr Opin Biotechnol 13:578

    Article  CAS  Google Scholar 

  18. Pamies O, Ell AH, Samec JSM, Hermanns N, Bäckvall J-E (2002) Tetrahedron Lett 43:4699B1;ndash;4702

    Article  CAS  Google Scholar 

  19. Casey CP, Singer SW, Powell DR, Hayashi RK, Kavana M (2001) J Am Chem Soc 123:1090B1;ndash;1100

    Article  CAS  Google Scholar 

  20. Csjernyik G, Ell AH, Fadini L, Pugin B, Bäckvall J-E (2002) J Org Chem 67:1657B1;ndash;1662

    Article  CAS  Google Scholar 

  21. Yamakawa M, Ito H, Noyori R (2000) J Am Chem Soc 122:1466B1;ndash;1478

    Article  CAS  Google Scholar 

  22. Ikariya T, Murata K, Noyori R (2006) Org Biomol Chem 4:393B1;ndash;406

    Article  CAS  Google Scholar 

  23. Johnson JB, Bäckvall J-E (2003) J Org Chem 68:7681B1;ndash;7684

    Article  CAS  Google Scholar 

  24. Ell AH, Johnson JB, Bäckvall J-E (2003) Chem Commun:1652B1;ndash;1653

    Google Scholar 

  25. Samec JSM, éll AH, Åberg JB, Privalov T, Eriksson L, Bäckvall J-E (2006) J Am Chem Soc 128:14293B1;ndash;14305

    Article  CAS  Google Scholar 

  26. Samec JSM, éll AH, Bäckvall J-E (2004) Chem Commun:2748B1;ndash;2749

    Google Scholar 

  27. Åberg JB, Bäckvall J-E (2008) Chem Eur J 14:9169B1;ndash;9174

    Article  Google Scholar 

  28. Casey CP, Bikzhanova GA, Cui Q, Guzei IA (2005) J Am Chem Soc 127:14062B1;ndash;14071

    Article  CAS  Google Scholar 

  29. Casey CP, Clark TB, Guzei IA (2007) J Am Chem Soc 129:11821B1;ndash;11827

    Article  CAS  Google Scholar 

  30. Karvembu R, Prabhakaran R, Natarajan K (2005) Coord Chem Rev 249:911B1;ndash;918

    Article  CAS  Google Scholar 

  31. Samec JSM, Bäckvall J-E (2009) Hydroxytetraphenycyclopentadienyl(tetraphenyl-2,4-cyclopentadien-1-one)-B1;mu;-hydrotetracarbonyldiruthenium(II). In: Fuchs PL (ed) Encyclopedia of reagents for organic synthesis, vol 7, 2nd edn. Wiley, New York, pp 5557B1;ndash;5564

    Google Scholar 

  32. Conley BL, Pennington-Boggio MK, Boz E, Williams TJ (2010) Chem Rev 110:2294B1;ndash;2312

    Article  CAS  Google Scholar 

  33. Samec J, Bäckvall J-E, Andersson P, Brandt P (2006) Chem Soc Rev 35:237B1;ndash;248

    Article  CAS  Google Scholar 

  34. Comas-Vives A, Ujaque G, Lledós A (2009) J Mol Struct THEOCHEM 903:123B1;ndash;132

    Article  CAS  Google Scholar 

  35. Menashe N, Salant E, Shvo Y (1996) J Organomet Chem 514:97

    Article  CAS  Google Scholar 

  36. Leijondahl K, Fransson AB, Bäckvall J-E (2006) J Org Chem 71:8622

    Article  CAS  Google Scholar 

  37. Olofsson B, Bógar K, Fransson A-BL, Bäckvall J-E (2006) J Org Chem 71:8256

    Article  CAS  Google Scholar 

  38. Wang G-Z, Bäckvall J-E (1992) J Chem Soc Chem Commun:980

    Google Scholar 

  39. Shvo Y, Goldberg I, Czerkie D, Reshef D, Stein Z (1997) Organometallics 16:133

    Article  CAS  Google Scholar 

  40. Karlsson U, Wang G-Z, Bäckvall J-E (1994) J Org Chem 59:1196

    Article  CAS  Google Scholar 

  41. Wang GZ, Andreasson U, Bäckvall J-E (1994) Chem Commun:1037

    Google Scholar 

  42. Csernyik G, éll AH, Fadini L, Pugin B, Bäckvall J-E (2002) J Org Chem 67:1657

    Article  Google Scholar 

  43. Almeida MLS, Beller M, Wang G-Z, Bäckvall J-E (1996) Chem Eur J 12:1533

    Article  Google Scholar 

  44. Almeida MLS, Kocovský P, Bäckvall JE (1996) J Org Chem 61:6587

    Article  CAS  Google Scholar 

  45. Thorson MK, Klinkel KL, Wang J, Williams TJ (2009) Eur J Inorg Chem:295B1;ndash;302

    Google Scholar 

  46. Krumlinde P, BogB1;e_x00E1;r K, Bäckvall JE (2010) Chem Eur J 16:4031B1;ndash;4036

    Article  CAS  Google Scholar 

  47. Purse BW, Tran L-H, Piera J, B1;Aring;kermark B, Bäckvall J-E (2008) Chem Eur J 14:7500B1;ndash;7503

    Article  CAS  Google Scholar 

  48. Johnston EV, Karlsson EA, Tran L-H, B1;Aring;kermark B, Bäckvall J-E (2010) Eur J Org Chem:1971B1;ndash;1976.

    Google Scholar 

  49. Blacker AJ, Farah MM, Marsden SP, Saidi O, Williams JMJ (2009) Tetrahedron Lett 50:6106B1;ndash;6109

    Article  CAS  Google Scholar 

  50. Imm S, Bähn S, Tillack A, Mevius K, Neubert L, Beller M (2010) Chem Eur J 16:2705B1;ndash;2709

    Article  CAS  Google Scholar 

  51. Ebbers EJ, Ariaans GJA, Houbiers JPM, Bruggink A, Zwanenburg B (1997) Tetrahedron 53:9417B1;ndash;9476

    Article  CAS  Google Scholar 

  52. Thalén LK, Hedberg MH, Bäckvall J-E (2010) Tetrahedron Lett 51:6802B1;ndash;6805

    Article  Google Scholar 

  53. Casey CP, Johnson JB, Jiao X, Beetner SE, Singer SW (2010) Chem Commun 46:7915B1;ndash;7917

    Article  CAS  Google Scholar 

  54. Casey CP, Johnson JB (2005) Can J Chem 83:1339

    Article  CAS  Google Scholar 

  55. Casey CP, Vos TE, Bikzhanova GA (2003) Organometallics 22:901

    Article  CAS  Google Scholar 

  56. Casey CP, Guan H (2009) J Am Chem Soc 131:2499

    Article  CAS  Google Scholar 

  57. Casey CP, Johnson JB (2005) J Am Chem Soc 127:1883B1;ndash;1894

    Article  CAS  Google Scholar 

  58. Hollmann D, Jiao H, Spannenberg A, Bähn S, Tillack A, Parton R, Altink R, Beller M (2009) Organometallics 28:473B1;ndash;479

    Article  CAS  Google Scholar 

  59. Shvo Y, Abed M, Blum Y, Laine RM (1986) Isr J Chem 27:267B1;ndash;275

    CAS  Google Scholar 

  60. Rauk A, Allen LC, Mislow K (1970) Angew Chem Intl Ed Engl 9:400

    Article  CAS  Google Scholar 

  61. Bushweller CH, OB1;rsquo;Neil JW, Bilofsky HS (1972) Tetrahedron 28:2697

    Article  CAS  Google Scholar 

  62. Casey CP, Bikzhanova GA, Guzei IA (2006) J Am Chem Soc 128:2286B1;ndash;2293

    Article  CAS  Google Scholar 

  63. Privalov T, Samec JSM, Bäckvall J-E (2007) Organometallics 26:2840B1;ndash;2848

    Article  CAS  Google Scholar 

  64. Comas-Vives A, Ujaque G, Lledós A (2007) Organometallics 26:4135B1;ndash;4144

    Article  CAS  Google Scholar 

  65. Comas-Vives A, Ujaque G, Lledós A (2008) Organometallics 27:4854B1;ndash;4863

    Article  CAS  Google Scholar 

  66. Casey CP, Johnson JB, Singer SW, Cui Q (2005) J Am Chem Soc 127:3100B1;ndash;3109, Correction: J Am Chem Soc (2008) 130:1110

    Article  CAS  Google Scholar 

  67. Casey CP, Singer SW, Powell DR (2001) Can J Chem 79:1002B1;ndash;1011

    Article  CAS  Google Scholar 

  68. Casey CP, Beetner SE, Johnson JB (2008) J Am Chem Soc 130:2285B1;ndash;2295

    Article  CAS  Google Scholar 

  69. Casey CP, Vos TE, Singer SW, Guzei IA (2002) Organometallics 21:5038B1;ndash;5046

    Article  CAS  Google Scholar 

  70. Casey CP, Strotman NA, Beetner SE, Johnson JB, Priebe DC, Vos TE, Khodavandi B, Guzei IA (2006) Organometallics 25:1230B1;ndash;1235

    Article  CAS  Google Scholar 

  71. Casey CP, Strotman NA, Beetner SE, Johnson JB, Priebe DC, Guzei IA (2006) Organometallics 25:1236B1;ndash;1244

    Article  CAS  Google Scholar 

  72. Casey CP, Guan H (2007) J Am Chem Soc 129:5816B1;ndash;5817

    Article  CAS  Google Scholar 

  73. Huerta FF, Laxmi SYR, Bäckvall J-E (2000) Org Lett 2:1037B1;ndash;1040

    Article  CAS  Google Scholar 

  74. PB1;agrave;mies O, Bäckvall J-E (2001) J Org Chem 66:4022B1;ndash;4025, Correction: J Org Chem (2002) 67:1418

    Article  Google Scholar 

  75. Pàmies O, Bäckvall J-E (2002) J Org Chem 67:1261B1;ndash;1265

    Article  Google Scholar 

  76. Runmo A-BL, Pàmies O, Faber K, Bäckvall J-E (2002) Tetrahedron Lett 43:2983B1;ndash;2986

    Article  CAS  Google Scholar 

  77. Pàmies O, Bäckvall J-E (2002) J Org Chem 67:9006B1;ndash;9010

    Article  Google Scholar 

  78. Hoyos P, Fernández M, Sinisterra JV, Alcántara AR (2006) J Org Chem 71:7632B1;ndash;7637

    Article  CAS  Google Scholar 

  79. Vallin KSA, Posaric DW, Hamersak Z, Svensson MA, Minidis ABE (2009) J Org Chem 74:9328B1;ndash;9336

    Article  CAS  Google Scholar 

  80. StrB1;uuml;bing D, Krumlinde P, Piera J, Bäckvall J-E (2007) Adv Synth Catal 349:1577B1;ndash;1581

    Article  Google Scholar 

  81. Atuu MR, Hossain MM (2007) Tetrahedron Lett 48:3875B1;ndash;3878

    Article  CAS  Google Scholar 

  82. Persson AB, Huerta FF, Bäckvall J-E (1999) J Org Chem 64:5237B1;ndash;5240

    Article  CAS  Google Scholar 

  83. Edin M, Steinreiber J, Bäckvall J-E (2004) Proc Natl Acad Sci USA 101:5761B1;ndash;5766

    Article  CAS  Google Scholar 

  84. MartB1;iacute;n-Matute B, Bäckvall J-E (2004) J Org Chem 69:9191B1;ndash;9195

    Article  Google Scholar 

  85. Fransson ABL, Xu Y, Leijondahl K, Bäckvall J-E (2006) J Org Chem 71:6309B1;ndash;6316

    Article  CAS  Google Scholar 

  86. Paetzold J, Bäckvall J-E (2005) J Am Chem Soc 127:17620B1;ndash;17621

    Article  CAS  Google Scholar 

  87. Veld MAJ, Hult K, Palmans ARA, Meijer EW (2007) Eur J Org Chem:5416B1;ndash;5421

    Google Scholar 

  88. Hoben CE, Kanupp L, Bäckvall J-E (2008) Tetrahedron Lett 49:977B1;ndash;979

    Article  CAS  Google Scholar 

  89. Thalén LK, Zhao D, Sortais J-B, Paetzold J, Hoben C, Bäckvall J-E (2009) Chem Eur J 15:3403B1;ndash;3410

    Article  Google Scholar 

  90. Shakeri M, EngstrB1;ouml;m K, SandstrB1;ouml;m AG, Bäckvall J-E (2010) ChemCatChem 2:534B1;ndash;538

    Article  CAS  Google Scholar 

  91. Thalén LK, Bäckvall J-E (2010) Beilstein J Org Chem 6:823B1;ndash;829

    Article  Google Scholar 

  92. Millet R, TrB1;auml;ff AM, Petrus ML, Bäckvall J-E (2010) J Am Chem Soc 132:15182B1;ndash;15184

    Article  CAS  Google Scholar 

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Author information

Authors and Affiliations

  1. Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-100 44, Stockholm, Sweden

    Madeleine C. Warner & Jan-E. Bäckvall

  2. Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, WI, USA

    Charles P. Casey

Authors
  1. Madeleine C. Warner
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  2. Charles P. Casey
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  3. Jan-E. Bäckvall
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Corresponding authors

Correspondence to Charles P. Casey or Jan-E. Bäckvall .

Editor information

Editors and Affiliations

  1. Graduate School of Science & Engineering, Dept. Applied Chemistry, Tokyo Institute of Technology, Ookayama 2-12-1, Tokyo, 152-8550, Japan

    Takao Ikariya

  2. Institute of Microbial Chemistry, Kamioosaki 3-14-23, Tokyo, 141-0021, Japan

    Masakatsu Shibasaki

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Warner, M.C., Casey, C.P., Bäckvall, JE. (2011). Shvo’s Catalyst in Hydrogen Transfer Reactions. In: Ikariya, T., Shibasaki, M. (eds) Bifunctional Molecular Catalysis. Topics in Organometallic Chemistry, vol 37. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3418_2011_7

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