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
Blum Y, Shvo Y (1984) Isr J Chem 24:144
Shvo Y, Czarkie D, Rahamim Y, Chodosh DF (1986) J Am Chem Soc 108:7400
Menashe N, Shvo Y (1991) Organometallics 10:3885
Samec JSM, Bäckvall J-E (2002) Chem Eur J 8:2955
Samec JSM, Mony L, Bäckvall J-E (2005) Can J Chem 83:909
Blum Y, Czarkie D, Rahamim Y, Shvo Y (1985) Organometallics 4:1459
Wang G-Z, Andreasson U, Bäckvall J-E (1994) J Chem Soc Chem Commun:1037
Almeida MLS, Beller M, Wang G-Z, Bäckvall J-E (1996) Chem Eur J 2:1533
Csjernyik G, éll AH, Fadini L, Pugin B, Bäckvall J-E (2002) J Org Chem 67:1657
éll AH, Samec JSM, Brasse C, Bäckvall J-E (2002) Chem Commun:1144
éll AH, Johnson JB, Bäckvall J-E (2003) Chem Commun:1652B1;ndash;1653
Samec JSM, éll AH, Bäckvall J-E (2005) Chem Eur J 11:2327
Larsson ALE, Persson BA, Bäckvall J-E (1997) Angew Chem Int Ed Engl 36:1211
Persson BA, Larsson ALE, Ray ML, Bäckvall J-E (1999) J Am Chem Soc 121:1645
Huerta FF, Minidis A, Bäckvall J-E (2001) Chem Soc Rev 30:321
Pámies O, Bäckvall J-E (2003) Chem Rev 103:3247
Kim MJ, Ahn Y, Park J (2002) Curr Opin Biotechnol 13:578
Pamies O, Ell AH, Samec JSM, Hermanns N, Bäckvall J-E (2002) Tetrahedron Lett 43:4699B1;ndash;4702
Casey CP, Singer SW, Powell DR, Hayashi RK, Kavana M (2001) J Am Chem Soc 123:1090B1;ndash;1100
Csjernyik G, Ell AH, Fadini L, Pugin B, Bäckvall J-E (2002) J Org Chem 67:1657B1;ndash;1662
Yamakawa M, Ito H, Noyori R (2000) J Am Chem Soc 122:1466B1;ndash;1478
Ikariya T, Murata K, Noyori R (2006) Org Biomol Chem 4:393B1;ndash;406
Johnson JB, Bäckvall J-E (2003) J Org Chem 68:7681B1;ndash;7684
Ell AH, Johnson JB, Bäckvall J-E (2003) Chem Commun:1652B1;ndash;1653
Samec JSM, éll AH, Åberg JB, Privalov T, Eriksson L, Bäckvall J-E (2006) J Am Chem Soc 128:14293B1;ndash;14305
Samec JSM, éll AH, Bäckvall J-E (2004) Chem Commun:2748B1;ndash;2749
Åberg JB, Bäckvall J-E (2008) Chem Eur J 14:9169B1;ndash;9174
Casey CP, Bikzhanova GA, Cui Q, Guzei IA (2005) J Am Chem Soc 127:14062B1;ndash;14071
Casey CP, Clark TB, Guzei IA (2007) J Am Chem Soc 129:11821B1;ndash;11827
Karvembu R, Prabhakaran R, Natarajan K (2005) Coord Chem Rev 249:911B1;ndash;918
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
Conley BL, Pennington-Boggio MK, Boz E, Williams TJ (2010) Chem Rev 110:2294B1;ndash;2312
Samec J, Bäckvall J-E, Andersson P, Brandt P (2006) Chem Soc Rev 35:237B1;ndash;248
Comas-Vives A, Ujaque G, Lledós A (2009) J Mol Struct THEOCHEM 903:123B1;ndash;132
Menashe N, Salant E, Shvo Y (1996) J Organomet Chem 514:97
Leijondahl K, Fransson AB, Bäckvall J-E (2006) J Org Chem 71:8622
Olofsson B, Bógar K, Fransson A-BL, Bäckvall J-E (2006) J Org Chem 71:8256
Wang G-Z, Bäckvall J-E (1992) J Chem Soc Chem Commun:980
Shvo Y, Goldberg I, Czerkie D, Reshef D, Stein Z (1997) Organometallics 16:133
Karlsson U, Wang G-Z, Bäckvall J-E (1994) J Org Chem 59:1196
Wang GZ, Andreasson U, Bäckvall J-E (1994) Chem Commun:1037
Csernyik G, éll AH, Fadini L, Pugin B, Bäckvall J-E (2002) J Org Chem 67:1657
Almeida MLS, Beller M, Wang G-Z, Bäckvall J-E (1996) Chem Eur J 12:1533
Almeida MLS, Kocovský P, Bäckvall JE (1996) J Org Chem 61:6587
Thorson MK, Klinkel KL, Wang J, Williams TJ (2009) Eur J Inorg Chem:295B1;ndash;302
Krumlinde P, BogB1;e_x00E1;r K, Bäckvall JE (2010) Chem Eur J 16:4031B1;ndash;4036
Purse BW, Tran L-H, Piera J, B1;Aring;kermark B, Bäckvall J-E (2008) Chem Eur J 14:7500B1;ndash;7503
Johnston EV, Karlsson EA, Tran L-H, B1;Aring;kermark B, Bäckvall J-E (2010) Eur J Org Chem:1971B1;ndash;1976.
Blacker AJ, Farah MM, Marsden SP, Saidi O, Williams JMJ (2009) Tetrahedron Lett 50:6106B1;ndash;6109
Imm S, Bähn S, Tillack A, Mevius K, Neubert L, Beller M (2010) Chem Eur J 16:2705B1;ndash;2709
Ebbers EJ, Ariaans GJA, Houbiers JPM, Bruggink A, Zwanenburg B (1997) Tetrahedron 53:9417B1;ndash;9476
Thalén LK, Hedberg MH, Bäckvall J-E (2010) Tetrahedron Lett 51:6802B1;ndash;6805
Casey CP, Johnson JB, Jiao X, Beetner SE, Singer SW (2010) Chem Commun 46:7915B1;ndash;7917
Casey CP, Johnson JB (2005) Can J Chem 83:1339
Casey CP, Vos TE, Bikzhanova GA (2003) Organometallics 22:901
Casey CP, Guan H (2009) J Am Chem Soc 131:2499
Casey CP, Johnson JB (2005) J Am Chem Soc 127:1883B1;ndash;1894
Hollmann D, Jiao H, Spannenberg A, Bähn S, Tillack A, Parton R, Altink R, Beller M (2009) Organometallics 28:473B1;ndash;479
Shvo Y, Abed M, Blum Y, Laine RM (1986) Isr J Chem 27:267B1;ndash;275
Rauk A, Allen LC, Mislow K (1970) Angew Chem Intl Ed Engl 9:400
Bushweller CH, OB1;rsquo;Neil JW, Bilofsky HS (1972) Tetrahedron 28:2697
Casey CP, Bikzhanova GA, Guzei IA (2006) J Am Chem Soc 128:2286B1;ndash;2293
Privalov T, Samec JSM, Bäckvall J-E (2007) Organometallics 26:2840B1;ndash;2848
Comas-Vives A, Ujaque G, Lledós A (2007) Organometallics 26:4135B1;ndash;4144
Comas-Vives A, Ujaque G, Lledós A (2008) Organometallics 27:4854B1;ndash;4863
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
Casey CP, Singer SW, Powell DR (2001) Can J Chem 79:1002B1;ndash;1011
Casey CP, Beetner SE, Johnson JB (2008) J Am Chem Soc 130:2285B1;ndash;2295
Casey CP, Vos TE, Singer SW, Guzei IA (2002) Organometallics 21:5038B1;ndash;5046
Casey CP, Strotman NA, Beetner SE, Johnson JB, Priebe DC, Vos TE, Khodavandi B, Guzei IA (2006) Organometallics 25:1230B1;ndash;1235
Casey CP, Strotman NA, Beetner SE, Johnson JB, Priebe DC, Guzei IA (2006) Organometallics 25:1236B1;ndash;1244
Casey CP, Guan H (2007) J Am Chem Soc 129:5816B1;ndash;5817
Huerta FF, Laxmi SYR, Bäckvall J-E (2000) Org Lett 2:1037B1;ndash;1040
PB1;agrave;mies O, Bäckvall J-E (2001) J Org Chem 66:4022B1;ndash;4025, Correction: J Org Chem (2002) 67:1418
Pàmies O, Bäckvall J-E (2002) J Org Chem 67:1261B1;ndash;1265
Runmo A-BL, Pàmies O, Faber K, Bäckvall J-E (2002) Tetrahedron Lett 43:2983B1;ndash;2986
Pàmies O, Bäckvall J-E (2002) J Org Chem 67:9006B1;ndash;9010
Hoyos P, Fernández M, Sinisterra JV, Alcántara AR (2006) J Org Chem 71:7632B1;ndash;7637
Vallin KSA, Posaric DW, Hamersak Z, Svensson MA, Minidis ABE (2009) J Org Chem 74:9328B1;ndash;9336
StrB1;uuml;bing D, Krumlinde P, Piera J, Bäckvall J-E (2007) Adv Synth Catal 349:1577B1;ndash;1581
Atuu MR, Hossain MM (2007) Tetrahedron Lett 48:3875B1;ndash;3878
Persson AB, Huerta FF, Bäckvall J-E (1999) J Org Chem 64:5237B1;ndash;5240
Edin M, Steinreiber J, Bäckvall J-E (2004) Proc Natl Acad Sci USA 101:5761B1;ndash;5766
MartB1;iacute;n-Matute B, Bäckvall J-E (2004) J Org Chem 69:9191B1;ndash;9195
Fransson ABL, Xu Y, Leijondahl K, Bäckvall J-E (2006) J Org Chem 71:6309B1;ndash;6316
Paetzold J, Bäckvall J-E (2005) J Am Chem Soc 127:17620B1;ndash;17621
Veld MAJ, Hult K, Palmans ARA, Meijer EW (2007) Eur J Org Chem:5416B1;ndash;5421
Hoben CE, Kanupp L, Bäckvall J-E (2008) Tetrahedron Lett 49:977B1;ndash;979
Thalén LK, Zhao D, Sortais J-B, Paetzold J, Hoben C, Bäckvall J-E (2009) Chem Eur J 15:3403B1;ndash;3410
Shakeri M, EngstrB1;ouml;m K, SandstrB1;ouml;m AG, Bäckvall J-E (2010) ChemCatChem 2:534B1;ndash;538
Thalén LK, Bäckvall J-E (2010) Beilstein J Org Chem 6:823B1;ndash;829
Millet R, TrB1;auml;ff AM, Petrus ML, Bäckvall J-E (2010) J Am Chem Soc 132:15182B1;ndash;15184
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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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DOI: https://doi.org/10.1007/3418_2011_7
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