Nozaki–Hiyama–Kishi reaction
Cr-Ni双金属催化下烯基，炔丙基，炔基卤代物先氧化加成得到有机三价铬试剂，然后对醛进行亲核加成得到醇的反应。
催化循环
反应实例
参考文献
1. (a) Okude, C. T.; Hirano, S.; Hiyama, T.; Nozaki, H. J. Am. Chem. Soc. 1977, 99, 3179-3181. Hitosi Nozaki and T. Hiyama are professors at the Japanese Academy. (b) Takai, K.; Kimura, K.; Kuroda, T.; Hiyama, T.; Nozaki, H. Tetrahedron Lett. 1983, 24, 5281-5284. Kazuhiko Takai was Prof. Nozaki’s student during the discovery of the reaction and is a professor at Okayama University. (c) Jin, H.; Uenishi, J.; Christ, W. J.; Kishi, Y. J. Am. Chem. Soc. 1986, 108, 5644-5646. Yoshito Kishi at Harvard independently discovered the catalytic effect of nickel during his total synthesis of polytoxin. (d) Takai, K.; Tagahira, M.; Kuroda, T.; Oshima, K.; Utimoto, K.; Nozaki, H. J. Am. Chem. Soc. 1986, 108, 60486050. (e) Kress, M. H.; Ruel, R.; Miller, L. W. H.; Kishi, Y. Tetrahedron Lett. 1993, 34, 5999-6002.
2. Fürstner, A.; Shi, N. J. Am. Chem. Soc. 1996, 118, 12349-12357. (The catalytic cycle).
3. Chakraborty, T. K.; Suresh, V. R. Chem. Lett. 1997, 565-566.
4. Fürstner, A. Chem. Rev. 1999, 99, 991-1046. (Review).
5. Blaauw, R. H.; Benningshof, J. C. J.; van Ginkel, A. E.; van Maarseveen, J. H.;
Hiemstra, H. J. Chem. Soc., Perkin Trans. 1 2001, 2250-2256.
6. Berkessel, A.; Menche, D.; Sklorz, C. A.; Schroder, M.; Paterson, I. Angew. Chem. Int. Ed. 2003, 42, 1032-1035.
7. Takai, K. Org. React. 2004, 64, 253-612. (Review).
8. Karpov, G. V.; Popik, V. V. J. Am. Chem. Soc. 2007, 129, 3792-3793.
9. Valente, C.; Organ, M. G. Chem. Eur. J. 2008, 14, 8239-8245.
10. Yet, L. Nozaki–Hiyama–Kishi reaction. In Name Reactions for Homologations-Part I; Li, J. J., Ed.; Wiley: Hoboken, NJ, 2009, pp 299-318. (Review).
11. Austad, B. C.; Benayoud, F.; Calkins, T. L.; et al. Synlett 2013, 17, 327–332.
编译自：Name Reactions （A Collection of Detailed Reaction Mechanisms）, Jie Jack Li, Nozaki–Hiyama–Kishi reaction，page 443-444.
之前发布有关此反应的文章，主要介绍是加入锰还原三价铬使二价铬再生，参与反应。1977 年Tamejiro Hiyama和Hitoshi Nozaki首先发现此反应，之前的方法是还原三价铬盐得到二价铬盐直接进行反应，只不过之前的底物是烯丙基卤代物，到1983年底物扩展到烯基和芳基卤代物，后来发现是由于反应中混入了镍杂质的原因。1986年Yoshito Kishi 在哈佛大学进行polytoxin全合成的时候发现了氯化镍在此反应中的作用。
Nozaki-Hiyama反应
2016-03-25 有机合成
铬诱导下卤代烷和醛进行偶联的氧化还原反应。此反应的优点就是对醛有很高的化学选择性，缺点就是利用大量的有毒的铬盐。
此反应的新方法是只需要催化量的二价铬盐，加入锰进行还原使催化剂再生。
反应机理
催化量反应机理:
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编译自: Organic Chemistry Portal