Baran试剂

Baran试剂，二烷基亚磺酸锌盐，可以直接对杂环芳烃C-H键进行官能团化。现在很多Baran试剂都可以买到。6,7

反应机理

一种机理如下，形成CF3自由基参与反应。5

另外一种反应速率完全不同的机理也被观察到，此机理现在还在研究阶段。10

反应实例

咖啡因的二氟甲基化。

Baran试剂对喹啉的两个氢连续进行官能团化。

利用Langlois试剂（三氟甲烷亚磺酸钠）进官能团化。

参考文献

1. Tordeux, M.; Langlois, B.; Wakselman, C. J. Chem. Soc., Perkin Trans. 1 1990,2293–2299.

2. Langlois, B. R.; Laurent, E.; Roidot, N. Tetrahedron Lett. 1991, 32, 7525–7528.

3. Clavel, J. L.; Langlois, B.; Laurent, E.; Roidot, N. Phosphorus, Sulfur, and Silicon 1991, 58, 463–466.

4. Kino, T.; Nagase, Y.; Ohtsuka, Y.; Yamamoto, K.; Uraguchi, D.; Tokuhisa, K.;

Yamakawa, T. J. Fluorine Chem. 2010, 131, 98–105.

5. Ji, Y.; Brueckl, T.; Baxter, R. D.; Fujiwara, Y.; Seiple, I. B.; Su, S.; Blackmond, D. G.; Baran, P. S. Proc. Natl. Acad. Sci. U. S. A. 2011, 108, 14411–14415. Phil S. Baran is currently a Professor in the Department of Chemistry at The Scripps Research Institute and Member of The Skaggs Institute for Chemical Biology. He was born in New Jersey in 1977, received his B.S. in chemistry from NYU in 1997, his Ph.D. at The Scripps Research Institute in 2001 (NSF fellow with K.C. Nicolaou), and from 2001–2003 he was an NIH postdoctoral fellow at Harvard in the laboratory of E. J. Corey. He has published over 120 scientific articles (H-Factor = 40) and has recently released a book in heterocyclic chemistry. His laboratory is focused on the invention of new reactions of broad utility and synthesizing complex natural products in a scalable, economic fashion. He recently won the John D. and Catharine T. MacArthur award. 【Phil S. Baran现任斯克利普斯研究所教授，斯卡格化学生物学研究所成员。他1977年出生于新泽西州，1997年获得纽约大学的化学学士学位，2001年在斯克利普斯研究所获得Ph.D.（在美国全国卫生基金会与 K.C. Nicolaou是同事）。2001年到2003年在哈佛大学E. J. Corey的实验室读美国国立卫生研究院博士后。他发表了超过120篇学术论文（H因子=40），最近还出版了一本杂环化学方面的书。他的实验室主要研究方向是开发新反应的更广的应用领域和利用更容易操作的成本低得新方法合成复杂的天然产物。他最近获得了John D. and Catharine T. MacArthur奖。】

6. Fujiwara, Y.; Dixon, J. A.; Rodriguez, R. A.; Baxter, R. D.; Dixon, D. D.; Collins, M.R.; Blackmond, D. G.; Baran, P. S. J. Am. Chem. Soc. 2012, 134, 1494–1497.

7. Fujiwara, Y.; Dixon, J. A.; O’Hara, F.; Funder, E. D.; Dixon, D. D.; Rodriguez, R. A.; Baxter, R. D.; Herle, B.; Sach, N.; Collins, M. R.; Ishihara, Y.; Baran, P. S. Nature 2012, 492, 95–99.

8. Zhou, Q.; Ruffoni, A.; Gianatassio, R.; Fujiwara, Y.; Sella, E.; Shabat, D.; Baran, P. S. Angew. Chem. Int. Ed. 2013, 52, 3949–3952

9. O’Hara, F.; Baxter, R. D.; O’Brien, A. G.; Collins, M. R.; Dixon, J. A.; Fujiwara, Y.; Ishihara, Y.; Baran, P. S. Nature Protocols 2013, 8, 1042–1047.

10. Baxter, R. D.; Blackmond, D. G. Tetrahedron 2013, 69, 5604–5608.

11. O’Hara, F.; Blackmond, D. G.; Baran, P. S. J. Am. Chem. Soc. 2013, 135, 12122–12134.

编译自：J.J. Li, Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications, Baran reagents，page 18-20.