Visible-light-mediated interrupted Cloke-Wilson rearrangement of cyclopropyl ketones to construct oxy-bridged macrocyclic framework

Tetrahedron Chem

Yin Wei¹  Zhen Liu²  Min Shi³ 

[1] Molecular Engineering, East China University of Science and Technology, Meilong Road No.130, Shanghai, 200237, China;;Key Laboratory for Advanced Materials and Institute of Fine Chemicals, Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry &State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China;

关键词: Cyclopropyl ketones;    Visible-light-induced;    Interrupted Cloke−Wilson rearrangement;    Oxy-bridged macrocycle;    Indolinones;   

DOI  :  

来源: DOAJ

【 摘 要 】

Cloke-Wilson rearrangement has been well studied, in which cyclopropyl ketones or cyclopropyl imines could be transformed to dihydrofuran or dihydropyrrole derivatives through a tandem ring-opening/recyclization process. Herein, we report a new version of Cloke-Wilson rearrangement, in which the ring-opening/recyclization of cyclopropyl ketones upon visible-light-induced photoredox catalysis can provide oxy-bridged macrocyclic frameworks under mild reaction conditions, and the reagent XRf plays dual roles in the catalytic cycle. The reaction proceeds through a ring-opening and an interrupted recyclization by intramolecular nucleophilic attack with the in situ generated radical cation. The reaction mechanism was proposed on the basis of control, deuterium labeling, Stern–Volmer quenching and CV measuring experiments. This protocol can afford a series of oxy-bridged macrocyclic frameworks with broad substrate scope and good functional-group tolerance. In addition, a variety of 2,2-disubstituted oxy-bridged macrocyclic indolinones can be obtained efficiently by simple manipulation from the products.

【 授权许可】

Unknown