Liu Yanjie, Fan Xinran, Tian Rongqiang, Duan Zheng
College of Chemistry, Green Catalysis Center, International Phosphorus Laboratory, International Joint Research Laboratory for Functional Organophosphorus Materials of Henan Province, Zhengzhou University, Zhengzhou 450001, PR China.
Org Lett. 2021 Apr 16;23(8):2943-2947. doi: 10.1021/acs.orglett.1c00602. Epub 2021 Mar 29.
We have developed an unprecedented approach for the synthesis of transient 1-phosphafulvenes through three component reactions of phospholes. The generation of 1-phosphafulvenes was demonstrated by in situ [6 + 4] cycloaddition with 2-phospholes and [6 + 6] self-dimerization. The [6 + 4] and [6 + 6] reaction pathway could be modulated by the starting ketones and aldehydes. The construction of 1-phosphafulvenes is illustrated by a proposed mechanism combining nucleophilic addition of phospholide to the iminium or isomerized azomethine ylide and a [1,5]-shift of phosphole.
我们通过磷杂环戊二烯的三组分反应开发了一种前所未有的合成瞬态1-磷杂富烯的方法。通过与2-磷杂环戊二烯的原位[6 + 4]环加成反应和[6 + 6]自二聚反应证明了1-磷杂富烯的生成。[6 + 4]和[6 + 6]反应途径可通过起始酮和醛进行调节。通过将磷叶立德对亚胺鎓或异构化甲亚胺叶立德的亲核加成与磷杂环戊二烯的[1,5]迁移相结合的拟议机理说明了1-磷杂富烯的构建。
