利用硼烷和手性惡唑硼烷催化劑（CBS catalyst）對(duì)映異構(gòu)選擇性的還原酮得到相應(yīng)的手性醇。通常情況下，MeCBS比較常用 (R'' = Me,通過改變?nèi)〈梢栽黾舆x擇性)。
反應(yīng)機(jī)理：
反應(yīng)機(jī)理表明此反應(yīng)的高對(duì)映異構(gòu)選擇性和高反應(yīng)速率，只受CBS催化劑的影響。次催化劑既作為手性助劑也作為 Lewis 酸參與反應(yīng)。
最新文獻(xiàn)：
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.
編譯自：Organic Chemistry Portal
相關(guān)介紹
Corey–Bakshi–Shibata (CBS)試劑是一種由脯氨酸制備而來的手性催化劑。又被稱為Corey惡唑硼烷 ，可以和硼烷共用對(duì)映選擇性的還原酮，催化不對(duì)稱的Diels–Alder反應(yīng)和 [3 + 2]環(huán)加成。
試劑的制備
機(jī)理和催化循環(huán)
反應(yīng)實(shí)例
參考文獻(xiàn)
1. (a) Corey, E. J.; Bakshi, R. K.; Shibata, S. J. Am. Chem. Soc. 1987, 109, 5551–5553.
(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.
2. Reviews: (a) Corey, E. J. Pure Appl. Chem. 1990, 62, 1209–1216. (b) Wallbaum, S.;Martens, J. Tetrahedron: Asymm. 1992, 3, 1475–1504. (c) Singh, V. K. Synthesis 1992, 605–617. (d) Deloux, L.; Srebnik, M. Chem. Rev. 1993, 93, 763–784. (e) Taraba, M.; Palecek, J. Chem. Listy 1997, 91, 9–22. (f) Corey, E. J.; Helal, C. J.Angew. Chem. Int. Ed. 1998, 37, 1986–2012. g) Corey, E. J. Angew. Chem. Int. Ed. 2002, 41, 1650–1667. (h) Itsuno, S. Org. React. 1998, 52, 395–576. (i) Cho, B. T. Aldrichimica Acta 2002, 35, 3–16. (j) Glushkov, V. A.; Tolstikov, A. G. Russ. Chem. Rev. 2004, 73, 581–608. (k) Cho, B .T. Tetrahedron 2006, 62, 7621–7643.
3. (a) Mathre, D. J.; Thompson, A. S.; Douglas, A. W.; Hoogsteen, K.; Carroll, J. D.; Corley, E. G.; Grabowski, E. J. J. J. Org. Chem. 1993, 58, 2880–2888. (b) Xavier, L.C.; Mohan, J. J.; Mathre, D. J.; Thompson, A. S.; Carroll, J. D.; Corley, E. G.; Desmond,R. Org. Synth. 1997, 74, 50–71.
4. Corey, E. J.; Helal, C. J. Tetrahedron Lett. 1996, 37, 4837–4840.
5. Clark, W. M.; Tickner-Eldridge, A. M.; Huang, G. K.; Pridgen, L. N.; Olsen, M. A.;Mills, R. J.; Lantos, I.; Baine, N. H. J. Am. Chem. Soc. 1998, 120, 4550–4551.
6. Cho, B. T.; Kim, D. J. Tetrahedron: Asymmetry 2001, 12, 2043–2047.
7. Price, M. D.; Sui, J. K.; Kurth, M. J.; Schore, N. E. J. Org. Chem. 2002, 67, 8086–8089.
8. Degni, S.; Wilen, C.-E.; Rosling, A. Tetrahedron: Asymmetry 2004, 15, 1495–1499.
9. Watanabe, H.; Iwamoto, M.; Nakada, M. J. Org. Chem. 2005, 70, 4652–4658.
10. Zhou, G.; Corey, E. J. J. Am. Chem. Soc. 2005, 127, 11958–11959.
11. Yeung, Y.-Y.; Hong, S.; Corey, E. J. J. Am. Chem. Soc. 2006, 128, 6310–6311.
12. Patti, A.; Pedotti, S. Tetrahedron: Asymmetry 2008, 19, 1891–1897.
13. Sridhar, Y.; Srihari, P. Eur. J. Org. Chem. 2013, 578–587.
編譯自：J.J. Li, Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications, Corey–Bakshi–Shibata (CBS) reagent，page 168-169.
