Burés Jordi, Isart Carles, Vilarrasa Jaume
Departament de Química Orgànica, Facultat de Química, Universitat de Barcelona, Diagonal 647, 08028 Barcelona, Catalonia, Spain.
Org Lett. 2009 Oct 1;11(19):4414-7. doi: 10.1021/ol9017722.
A new variant of the NO(2)-to-CO transformation (the Nef reaction) that occurs at room temperature under neutral conditions is uncovered. After the conversion of secondary nitroalkanes to phenylsulfenylketimines, these thiooximes are hydrolyzed quantitatively in situ, in THF-H(2)O at pH 7, by addition of AuBr(3) (but not with other MX(n)!). Adducts arising from asymmetric nitro-Michael and nitro-aldol reactions afford 1,4-diketones and alpha-alkoxy ketones, respectively, with full retention of the configuration of the stereocenters alpha to the CHNO(2)/C=N-SPh/C=O groups.
发现了一种在室温中性条件下发生的从二氧化氮到一氧化碳转化（内夫反应）的新变体。仲硝基烷烃转化为苯亚磺酰基酮亚胺后，通过添加三溴化金（而不是其他MXₙ！），这些硫代肟在pH为7的四氢呋喃 - 水体系中在原位被定量水解。不对称硝基 - 迈克尔反应和硝基 - 羟醛反应产生的加合物分别得到1,4 - 二酮和α - 烷氧基酮，与CHNO₂/C=N - SPh/C=O基团α位的立体中心构型完全保持一致。
