コーリー・バクシ・柴田還元とは - わかりやすく解説 Weblio辞書

コーリー・バクシ・柴田還元

出典: フリー百科事典『ウィキペディア（Wikipedia）』 (2024/01/23 08:19 UTC 版)

コーリー・バクシ・柴田還元（コーリー・バクシ・しばたかんげん、Corey-Bakshi-Shibata reduction）は、キラルなオキサザボロリジンを触媒としてボランにより光学不活性ケトンを不斉還元して光学活性な2級アルコールを得る還元反応のことである。CBS還元と略されることも多い。1987年にイライアス・コーリー、ラマン・バクシ、柴田サイゾウによって報告された^[1]^[2]。オキサボロリジンを用いたケトンの不斉還元は、これ以前の1981年に伊津野真一らによって報告されている^[3]。

脚注

^ ^a ^b ^c Corey, E. J.; Bakshi, R. K.; Shibata, S. (1987). “Highly enantioselective borane reduction of ketones catalyzed by chiral oxazaborolidines. Mechanism and synthetic implications”. J. Am. Chem. Soc. 109: 5551. doi:10.1021/ja00252a056.
^ ^a ^b ^c Corey, E. J.; Bakshi, R. K.; Shibata, S.; Chen, C. P.; Singh, V. K. (1987). “A stable and easily prepared catalyst for the enantioselective reduction of ketones. Applications to multistep syntheses”. J. Am. Chem. Soc. 109: 7925. doi:10.1021/ja00259a075.
^ ^a ^b Hirao, A.; Itsuno, S.; Nakahama, S.; Yamazaki, N. (1981). “Asymmetric reduction of aromatic ketones with chiral alkoxy-amineborane complexes”. J. Chem. Soc., Chem. Commun. 7: 315. doi:10.1039/C39810000315.
^ Deloux, L.; Srebnik, M. (1993). “Asymmetric boron-catalyzed reactions”. Chem. Rev. 93: 763. doi:10.1021/cr00018a007.
^ ^a ^b ^c ^d ^e ^f ^g ^h Corey, E. J.; Helal, C. J. (1998). “Reduction of Carbonyl Compounds with Chiral Oxazaborolidine Catalysts: A New Paradigm for Enantioselective Catalysis and a Powerful New Synthetic Method”. Angew. Chem. Int. Ed. 37: 1986. doi:10.1002/(sici)1521-3773(19980817)37:15<1986::aid-anie1986>3.0.co;2-z.
^ ^a ^b Cho, B. T. (2006). “Recent advances in the synthetic applications of the oxazaborolidine-mediated asymmetric reduction”. Tetrahedron 62: 7621. doi:10.1016/j.tet.2006.05.036.
^ Itsuno, S.; Hirao, A.; Nakahama, S.; Yamazaki, N. (1983). “Asymmetric synthesis using chirally modified borohydrides. Part 1. Enantioselective reduction of aromatic ketones with the reagent prepared from borane and (S)-valinol”. J. Chem. Soc., Perkin Trans. 1: 1673-1676. doi:10.1039/P19830001673.
^ Itsuno, S.; Ito, K.; Hirao, A.; Nakahama, S. (1983). “Asymmetric reduction of aromatic ketones with the reagent prepared from (S)-(–)-2-amino-3-methyl-1,1-diphenylbutan-1-ol and borane”. J. Chem. Soc., Chem. Commun. 8: 469-470. doi:10.1039/C39830000469.
^ Corey, E. J.; Azimioara, M.; Sarshar, S. (1992). “X-Ray crystal structure of a chiral oxazaborolidine catalyst for enantioselective carbonyl reduction”. Tetrahedron Lett. 33: 3429. doi:10.1016/s0040-4039(00)92654-6.
^ Evans, D. (1988). “Stereoselective organic reactions: catalysts for carbonyl addition processes”. Science 240: 420. doi:10.1126/science.3358127.
^ Jones, D. K.; Liotta, D. C.; Shinkai, I.; Mathre, D. J. (1993). “Origins of the enantioselectivity observed in oxazaborolidine-catalyzed reductions of ketones”. J. Org. Chem. 58: 799. doi:10.1021/jo00056a001.
^ Corey, E. J. (1990). “New enantioselective routes to biologically interesting compounds”. Pure Appl. Chem. 62: 1209. doi:10.1351/pac199062071209.
^ Nevalainen, V. (1994). “Quantum chemical modeling of chiral catalysis. Part 15. On the role of hydride-bridged borane - alkoxyborane complexes in the catalytic enantioselective reduction of ketones promoted by chiral oxazaborolidines”. Tetrahedron: Asymmetry 5: 289. doi:10.1016/s0957-4166(00)86186-8.
^ Quallich, G. J.; Blake, J. F.; Woodall, T. M. (1994). “A combined synthetic and ab initio study of chiral oxazaborolidines structure and enantioselectivity relationships”. J. Am. Chem. Soc. 116: 8516. doi:10.1021/ja00098a012.
^ ^a ^b Quallich, G. J.; Woodall, T. M. (1993). “Enantioselective oxazaborolidine reduction of ketones containing heteroatoms”. Tetrahedron Lett. 34: 785. doi:10.1016/0040-4039(93)89012-f.
^ ^a ^b Jones, T. K.; Mohan, J. J.; Xavier, L. C.; Blacklock, T. J.; Mathre, D. J.; Sohar, P.; Jones, E. T. T.; Reamer, R. A.; Roberts, F. E.; Grabowski, E. J. J. (1991), “An asymmetric synthesis of MK-0417. Observations on oxazaborolidine-catalyzed reductions”, J. Org. Chem. 56: 763, doi:10.1021/jo00002a050
^ Bulliard, Michael (1999). “Chapter 11.1: Asymmtric Reduction of Prochiral Ketones Catalyzed by Oxazaborolidines”. In Ager, David. Handbook of Chiral Chemicals. Marcel Decker. pp. 211–225. ISBN 0824710584
^ Corey, E. J.; Link, J. O. (1989), “A new chiral catalyst for the enantioselective synthesis of secondary alcohols and deuterated primary alcohols by carbonyl reduction”, Tetrahedron Lett. 30: 6275, doi:10.1016/s0040-4039(01)93871-7
^ Corey, E. J.; Bakshi, R. K. (1990), “A new system for catalytic enantioselective reduction of achiral ketones to chiral alcohols. Synthesis of chiral α-hydroxy acids”, Tetrahedron Lett. 31: 611, doi:10.1016/s0040-4039(00)94581-7
^ Nettles, S. M.; Matos, K.; Burkhardt, E. R.; Rouda, D. R.; Corella, J. A. (2002), “Role of NaBH₄ Stabilizer in the Oxazaborolidine-Catalyzed Asymmetric Reduction of Ketones with BH₃-THF”, J. Org. Chem. 67: 2970, doi:10.1021/jo016257c
^ Stemmler, R. T. (2007), “CBS Oxazaborolidines - Versatile Catalysts for Asymmetric Synthesis”, Synlett 6: 997, doi:10.1055/s-2007-973876