Barton亚硝酸酯光解反应

光解亚硝酸酯得到δ-肟醇的反应。

该反应是在光照条件下，对醇δ位的非活性烷烃部位进行官能团化的手法。收率比较高，并且往往该方法可以对一般反应所不能的位置进行官能团导入，此方法的发现对甾体化学的发展是一个巨大的推动。

反应机理

反应经由RO–NO键均裂，氧自由基1,5-夺氢，由于氮氧自由基相对稳定，而后自由基结合得到亚硝基中间体，异构化得到产物。

反应实例

参考文献

1. (a) Barton, D. H. R.; Beaton, J. M.; Geller, L. E.; Pechet, M. M. J. Am. Chem. Soc. 1960, 82, 2640-􀀐2641. In 1960, Derek Barton took a “vacation” in Cambridge, Massachusetts; he worked in a small research institute called the Research Institute for Medicine and Chemistry. In order to make the adrenocortical hormone aldosterol, Barton invented the Barton nitrite photolysis by simply writing down on a piece of paper what he thought would be an ideal process. His skilled collaborator, Dr. John Beaton, was able to reduce it to practice. They were able to make 40 to 50 g of aldosterol at a time when the total world supply was only about 10 mg. Barton considered it his most satisfying piece of work.【1960年, Derek Barton在马萨诸塞州剑桥市一个很小的医药化学研究所工作。为了合成肾上腺皮质激素醛固酮，他想到了一个理想的光解亚硝酸酯的机理并简单的写在一张纸上。他的一个很有经验的合作者John Beaton博士，将其付诸实践。他们可以一次反应可以合成40到50g醛固酮，而当时全世界纯的醛固酮的量也就10mg。Barton也把这项】 (b) Barton, D. H. R.; Beaton, J. M. J. Am. Chem. Soc. 1960, 82,2641-􀀐2641. (c) Barton, D. H. R.; Beaton, J. M. J. Am. Chem. Soc. 1961, 83,4083-4089. (d) Barton, D. H. R.; Lier, E. F.; McGhie, J. M. J. Chem. Soc., (C) 1968, 1031-􀀐1040.

2. Nickon, A; Iwadare, T.; McGuire, F. J.; Mahajan, J. R; Narang, S. A.; Umezawa, B. J.Am. Chem. Soc. 1970, 92, 1688–1696.

3. Barton, D. H. R.; Hesse, R. H.; Pechet, M. M.; Smith, L. C. J. Chem. Soc., Perkin Trans. 1 1979, 1159􀀐-1165.

4. Barton, D. H. R. Aldrichimica Acta 1990, 23, 3-􀀐10. (Review).

5. Majetich, G.; Wheless, K. Tetrahedron 1995, 51, 7095􀀐-7129. (Review).

6. Sicinski, R. R.; Perlman, K. L.; Prahl, J.; Smith, C.; DeLuca, H. F. J. Med. Chem.1996, 22, 4497–4506.

7. Anikin, A.; Maslov, M.; Sieler, J.; Blaurock, S.; Baldamus, J.; Hennig, L.; Findeisen, M.; Reinhardt, G.; Oehme, R.; Welzel, P. Tetrahedron 2003, 59, 5295-􀀐5305.

8. Suginome, H. CRC Handbook of Organic Photochemistry and Photobiology 2nd edn.; 2004, 102/1􀀐-102/16. (Review).

9. Hagan, T. J. Barton nitrite photolysis. In Name Reactions for Homologations-Part I; Li, J. J., Ed.; Wiley: Hoboken, NJ, 2009, pp 633􀀐-647. (Review).

编译自：Name Reactions （A Collection of Detailed Reaction Mechanisms）, Jie Jack Li, Barton nitrite photolysis，page 30-31.