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噁唑硼烷对苯甲酮不对称还原反应催化性能的理论计算 被引量：3

Theoretical Study on Enantioselectivity of Oxazaborolidine Catalysts for Reduction of Phenyl Methyl Ketone
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摘要 采用AM1方法研究了四种1,3,2-噁唑硼烷催化剂对苯甲酮不对称还原反应的催化性能,计算了立体控制步骤中生成R和S型催化配合物的反应热和活化能,并根据立体控制步骤中R和S型过渡态的熵和焓等参数,计算了四种催化反应体系最终产物的绝对构型及光学活性(e.e.%),据此对四种催化剂的对映选择性作出了评价. The AM1-SCF MO method has been applied to study the enantioselectivities of four kinds of 1,3, 2-oxazaborolidine as the catalysts in the reduction of phenyl methyl ketone. The optimized geometries, thermal anthalpies and entropies of R and S transition states in the stereo-controlling steps of the four catalyzed-reductions have been obtained. The absolute configurations and optical activities （e. e. % values） of the final products are calculated. It was found that （S） -3-methyl-4-benzyl-5, 5-diphenyl-1,3, 2-oxazaborolidine shows better enantioselectity in the catalysts.
作者 樊建芬 黄洁 卢运祥 孙云鹏
机构地区 苏州大学化学系
出处 《化学研究》 CAS 2005年第3期58-61,共4页 Chemical Research
基金 苏州大学君政基金课题
关键词 AM1 苯甲酮 不对称还原反应 对映选择性 嗯唑硼烷催化剂 AM1 phenyl methyl ketone enantioselective reduction enantioselectivity oxazaborolidine catalyst
分类号 O641.12 [理学—物理化学]
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参考文献13

  • 1Corey E J, Bakshi R K, Shibata S. Highly enantioselective borane reduction of ketones catalyzed by chiral oxazaborolidines.Mechanism and synthetic implications [ J ]. J Am Chem Soc, 1987, 109 : 5551 - 5553.
  • 2Nevalainen V. 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 oxazaborolidinea [ J ]. Tetrahedron: Asymmetry,1994, 5: 289- 296.
  • 3Nevalainen V. Quantum chemical modeling of chiral catalysis. Part 13. On the role of borane O-adducts in the enantioselective reduction of ketones catalyzed by chiral oxazaborolidines [ J ]. Tetrahedron : Asymmetry, 1993, 4 : 2001 - 2010.
  • 4Nevalainen V. Quantum chemical modeling of chiral catalysis. Part 19. Strain and stability oxazadiboretanes potentially involved in the enantioselective reduction of ketones promoted by chiral oxazaborolidines [ J ]. Tetrahedron : Asymmetry, 1994, 5 : 903 -908.
  • 5Shen Z X, Huang W, Feng J W, et al. Chiral oxazaborolidines bearing a 1- or 2-naphthylmethyl group as catalysts for the enantioselective borane reduction of ketones : experimental and quantum chemical calculations [ J ]. Tetrahedron : Asymmetry, 1998, 9 :1091 - 1095.
  • 6孙成科,杨思娅,马思渝,李宗和.不对称硼催化反应的理论研究(Ⅰ)——噁唑硼烷催化苯基乙酮还原反应的对映体选择性机理[J].高等学校化学学报,2002,23(1):109-112. 被引量：8
  • 7樊建芬,沈宗旋,王秋霞,卢运祥,顾小芳,黄洁.苯甲酮不对称还原反应的理论研究[J].Chinese Journal of Structural Chemistry,2004,23(1):100-104. 被引量：5
  • 8Fan J F, Wang Q X, Lu Y X. Theoretical study on the optical activities of the final products in the enantioselective reductions of β-aminoketones[J]. J Mol Struct ( Theo Chem), 2004, 674:49-53.
  • 9Stewart J J P. A general molecular orbital package. QCPE 455, 6^th ed, 1988.
  • 10Dewar M J S, Zeobisch E G, Healy E F, et al. AMI: a new general purpose quantum mechanical molecular model [J]. J Am Chem Soc, 1985, 107 : 3902 -3909.

二级参考文献16

  • 1[7]Nevalainen, V. Tetrahedron: Asymmetry 1994, 5, 903-908.
  • 2[8]Shen, Z. X.; Huang, W.; Feng, J. W.; Zhang, Y. W. Tetrahedron: Asymmetry 1998, 9, 1091-1095.
  • 3[9]Corey, E. J.; Bakshi, R. K.; Shibata, S.; Chen, C. P.; Singh, V. K. J. Am. Chem. Soc. 1987, 109, 7925-7926.
  • 4[10]Stewart, J. J. P. Mopac. A General Molecular Orbital Package.QCPE 455, 6th edn. 1988.
  • 5[11]Dewar, M. J. S.; Zeobisch, E. G.; Healy, E. F.; Stewart, J. J. P. J. Am. Chem. Soc. 1985, 107, 3902-3909.
  • 6[12]Pople, J. A.; Beveridge, D. L. Approximate Molecular Orbital Theory. New York McGraw-Hill 1970.
  • 7[13]Baker, J. J. Comp. Chem. 1986, 7, 385-395.
  • 8[14]Zhang, Y. W.; Liang, J.; Lu, J.; Guo, C. L.; Shen, Z. X. J. Chinese. Org. Chem. 2000, 20, 334-337.
  • 9[1]Corey, E. J.; Bakshi, R. K. Tetrahedron Lett. 1990, 31, 611-614.
  • 10[2]Itsuno, S.; Hirao, A.; Nakahama, S. J. Chem. Soc. Chem. Commun. 1983, 469-470.

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化学研究
2005年 第3期

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