Corey-Bakshi-Shibata还原
利用硼烷和手性恶唑硼烷催化剂(CBS catalyst)对映异构选择性的还原酮得到相应的手性醇。通常情况下,MeCBS比较常用 (R'' = Me,通过改变取代基可以增加选择性)。
反应机理:
反应机理表明此反应的高对映异构选择性和高反应速率,只受CBS催化剂的影响。次催化剂既作为手性助剂也作为 Lewis 酸参与反应。
最新文献:
Practical enantioselective reduction of ketones using oxazaborolidine catalyst generated in situ from chiral lactam alcohol and borane
Y. Kawanami, S. Murao, T. Ohga, N. Kobayashi, Tetrahedron, 2003, 59, 8411-8414.
An Efficient and Catalytically Enantioselective Route to (S)-(-)-Phenyloxirane
E. J. Corey, S. Shibata, R. K. Bakshi, J. Org, Chem., 1988, 53, 2861-2863.
A novel enantioselective synthesis of α-amino acids has been developed, which is broad in scope, simple in application, and advantageous for many α-amino acids of interest in chemistry, biology, medicine.
E. J. Corey, J. O. Link, J. Am. Chem. Soc., 1992, 114, 1906-1908.
编译自:Organic Chemistry Portal
相关介绍
Corey–Bakshi–Shibata (CBS)试剂是一种由脯氨酸制备而来的手性催化剂。又被称为Corey恶唑硼烷 ,可以和硼烷共用对映选择性的还原酮,催化不对称的Diels–Alder反应和 [3 + 2]环加成。
试剂的制备
机理和催化循环
反应实例
参考文献
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(b) Corey, E. J.; Bakshi, R. K.; Shibata, S.; Chen, C.-P.; Singh, V. K. J. Am. Chem.Soc. 1987, 109, 7925–7926. (c) Corey, E. J.; Shibata, S.; Bakshi, R. K. J. Org. Chem.1988, 53, 2861–2863.
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编译自:J.J. Li, Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications, Corey–Bakshi–Shibata (CBS) reagent,page 168-169.