Department of Chemistry, Indian Institute of Science Education & Research, Bhopal, Madhya Pradesh, 462066, India.
Angew Chem Int Ed Engl. 2016 Jun 27;55(27):7831-5. doi: 10.1002/anie.201600878. Epub 2016 Mar 7.
A novel rhodium-catalyzed dienamine activation of diazoenals resulted in a new class of γ-functionalized donor-acceptor dienamines. The synthetic utility of these dienamines has been demonstrated in a cooperative rhodium(II)/Brønsted acid and gold(I)-catalyzed direct [3+3] annulation of enaldiazo ketones with N-propargyl anilines, thus leading to highly substituted enal-functionalized 1,4-oxazines. The reaction is proposed to involve dienamine activation through the diacceptor rhodium enalcarbenoid NH-insertion and a gold-catalyzed intramolecular site-selective 6-exo-dig heterocyclization. The methodology was applied to the efficient synthesis of structurally complex [1,4]oxazino[4,3-a]quinolone, which is present in the antibacterial agent PNU-286607.
一种新型的铑催化二氮烯醛的烯胺活化反应，生成了一类新型的γ-官能化给体-受体烯胺。这些烯胺的合成用途已在协同铑（II）/布朗斯台德酸和金（I）催化的烯二唑酮与 N-炔丙基苯胺的直接[3+3]稠环反应中得到了证明，从而得到了高度取代的烯醛官能化 1,4-恶嗪。该反应被认为涉及通过二受体铑烯醛卡宾 NH-插入和金催化的分子内选择性 6-endo-dig 杂环化来实现烯胺活化。该方法已成功应用于结构复杂的[1,4]恶嗪并[4,3-a]喹诺酮的高效合成，该化合物存在于抗菌剂 PNU-286607 中。
