Department of Chemistry and Centre for Theoretical and Computational Chemistry (CTCC), University of Tromsø, 9037, Tromsø, Norway.
Department of Chemistry, University of Tromsø, 9037, Tromsø, Norway.
Angew Chem Int Ed Engl. 2017 Apr 3;56(15):4277-4281. doi: 10.1002/anie.201610520. Epub 2017 Mar 20.
Metal carbenes can undergo a myriad of synthetic transformations. Sulfur ylides are potential safe precursors of metal carbenes. Herein, we report cascade reactions that involve carbenoids derived from sulfoxonium ylides for the efficient and regioselective synthesis of indoles and pyrroles. The tandem action of iridium and Brønsted acid catalysts enables rapid assembly of the heterocycles from unmodified anilines or readily accessible enamines under microwave irradiation. The key mechanistic steps are the catalytic transformation of the sulfoxonium ylide into an iridium-carbene complex, followed by N-H or C-H functionalization of an aniline or enamine, respectively, and a final acid-catalyzed cyclization. The present method was successfully applied to the synthesis of the densely functionalized pyrrole subunit of atorvastatin.
金属卡宾可以经历无数的合成转化。硫叶立德是金属卡宾的潜在安全前体。在此，我们报告了涉及源自亚砜叶立德的碳烯的级联反应，用于高效和区域选择性地合成吲哚和吡咯。铱和布朗斯台德酸催化剂的串联作用使杂环能够在微波照射下从未修饰的苯胺或容易获得的烯胺中快速组装。关键的机理步骤是亚砜叶立德催化转化为铱-卡宾配合物，然后分别对苯胺或烯胺进行 N-H 或 C-H 官能化，最后进行酸催化环化。本方法成功地应用于阿托伐他汀中稠合多功能化吡咯亚基的合成。
