Niu Zhi-Jie, Li Lian-Hua, Li Xue-Song, Liu Hong-Chao, Shi Wei-Yu, Liang Yong-Min
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, China.
Org Lett. 2021 Feb 19;23(4):1315-1320. doi: 10.1021/acs.orglett.0c04300. Epub 2021 Feb 3.
We developed a new transition-metal-free intermolecular Claisen rearrangement process to introduce allyl and allenyl groups into the α position of tertiary amides. In this transformation, amides were activated by trifluoromethanesulfonic anhydride to produce the keteniminium ion intermediates that exhibit strong electrophilic activity. This atom-economical process delivers α position-modified amides under mild conditions in moderate to good yields and showcases a broad substrate compatibility.
我们开发了一种新的无过渡金属分子间克莱森重排过程，将烯丙基和联烯基引入叔酰胺的α位。在这种转化中，酰胺被三氟甲磺酸酐活化，生成具有强亲电活性的烯酮亚胺离子中间体。这个原子经济的过程在温和条件下以中等至良好的产率提供α位修饰的酰胺，并展示了广泛的底物兼容性。
