Unusual Skeletal Reorganization of Oxetanes for the Synthesis of 1, 2‐Dihydroquinolines. Issue 28 (20th May 2020)

• Record Type: Journal Article
• Authors: Wang, Guannan; Huang, Hai; Guo, Wengang; Qian, Chenxiao; Sun, Jianwei
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 28(2020)
• Page Start: 11245
• Page End: 11249
• Publication Date: 2020-05-20
• Subjects: cyclization -- nitrogen heterocycles -- oxetane -- rearrangement -- strained molecules; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201916727
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Skeletal reorganization is a type of fascinating transformations owing to their intriguing mechanisms and utility in complex molecule synthesis. However, only a limited amount of examples are known for most functional groups. Herein, we describe such an unusual process of oxetanes. In the presence of In(OTf)3 as catalyst, oxetane‐tethered anilines reacted unexpectedly to form 1, 2‐dihydroquinolines. This process not only provides expedient access to dihydroquinolines, but also represents a new reaction of oxetane. Mechanistically, it is believed that the reaction proceeds through initial nitrogen attack rather than arene attack followed by a series of bond cleavage and formation events. Control experiments provided important insights into the mechanism. Abstract : An unusual skeletal reorganization of oxetanes is described, in which oxetane‐tethered anilines reacted unexpectedly to form 1, 2‐dihydroquinolines in the presence of In(OTf)3 as catalyst. This process proceeds through an intriguing mechanism involving a series of bond cleavage and formation steps.